CN116209147A

CN116209147A - Laminate, method for producing same, and copper wiring

Info

Publication number: CN116209147A
Application number: CN202310310339.0A
Authority: CN
Inventors: 斋藤正人; 汤本彻; 鹤田雅典
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2017-07-18
Filing date: 2018-07-18
Publication date: 2023-06-02
Also published as: KR102390722B1; US11109492B2; JP7345532B2; CN110870392B; JP2022009098A; KR20200015609A; TW201908138A; WO2019017363A1; JPWO2019017363A1; TWI691403B; EP3657916A4; CN110870392A; TW202003260A; EP3657916A1; US20200170125A1; TWI681872B; TW202003259A; JP7005625B2; TWI719646B

Abstract

The invention relates to a laminate, a method for manufacturing the laminate, and a copper wiring. A laminate is characterized by comprising a support, a coating layer comprising copper oxide and phosphorus disposed on a surface constituted by the support, and a resin layer disposed so as to cover the coating layer.

Description

Laminate, method for producing same, and copper wiring

The present application is a divisional application, the international application number of which is PCT/JP2018/026835, the international application date is 2018, 7, 18, the chinese country application number is 201880046322.6, and the date of entry into china is 2020, 1, 10, entitled "structure having conductive pattern region and method for manufacturing the same, laminate and method for manufacturing the same, and copper wiring".

Technical Field

The present invention relates to a structure having a conductive pattern region, a method for manufacturing the structure, a laminate, a method for manufacturing the laminate, and a copper wiring.

Background

The circuit board has a structure in which conductive wiring is provided on the board. The method for manufacturing the circuit board is generally as follows. First, a photoresist is coated on a substrate to which a metal foil is attached. Next, the photoresist is exposed and developed to obtain a desired floor-like shape of the circuit pattern. Next, the metal foil at the portion not covered with the photoresist is removed by chemical etching to form a pattern. Thus, a high-performance conductive substrate can be manufactured.

However, the conventional method has disadvantages such as a large number of steps, complexity, and the need for a photoresist material.

In contrast, a direct wiring printing technique of directly printing a desired wiring pattern on a substrate using a dispersion (hereinafter also referred to as a "paste material") in which particles selected from the group consisting of metal particles and metal oxide particles are dispersed has been attracting attention. The number of steps in this technique is small, and a photoresist material or the like is not required, so that productivity is extremely high.

As an example of the direct printing wiring technique, a technique is known in which a paste material is printed on a support by screen printing or inkjet printing, and then the paste material is thermally fired to obtain a wiring pattern having a low resistance (for example, see patent document 1).

There is also known a method of applying a paste material to the entire surface of a substrate, and applying laser light to the paste material in a pattern shape to selectively heat-fire the paste material, thereby obtaining a desired wiring pattern (see, for example, patent documents 1 and 2).

There is also known a method of manufacturing copper wiring by applying a dispersion liquid containing cuprous oxide aggregate particles to a polyethylene terephthalate (PET) support at a thickness of 10 to 20 μm and firing the dispersion liquid with a laser (see, for example, patent document 3). With this method, since the laser irradiation portion is not heated, a low heat-resistant resin material such as a PET support can be used.

In addition, a technique of using colloidal silica, which is silica particles, as a base layer in order to improve adhesion between a support and a metallic copper-containing film obtained by firing a copper paste is known (for example, see patent document 4).

In addition, the following methods for manufacturing a multilayer wiring board are known: a 1 st coating layer is formed on a substrate, a 1 st conductive portion is formed by irradiating a part of the 1 st coating layer with light, a 2 nd coating layer is formed on the 1 st coating layer, and a 2 nd conductive portion is formed by irradiating light from the 2 nd coating layer to the 1 st conductive portion (for example, see patent document 5).

In addition, a method of forming a patterned coating film using copper or copper oxide dispersion on a substrate and performing firing treatment to obtain a conductive film is known (for example, see patent document 6).

Prior art literature

Patent literature

Patent document 1: pamphlet of international publication No. 2010/024385

Patent document 2: japanese patent laid-open No. 5-37126

Patent document 3: japanese patent No. 5449154

Patent document 4: international publication 2016/031860 booklet

Patent document 5: japanese patent laid-open No. 2015-26681

Patent document 6: international publication No. 2015/012664 booklet

Disclosure of Invention

Problems to be solved by the invention

In the direct wiring printing technique for forming a wiring pattern by irradiating a paste material with laser light described in patent documents 1 to 3, unfired paste material remains in an area not irradiated with laser light. The unfired paste material has conductivity, and in this state, electrical insulation between wiring patterns cannot be ensured. Therefore, an operation of removing the unfired paste material and filling an insulating material such as a solder resist between the wiring patterns is performed.

Therefore, in the conventional direct wiring printing technology, a process for removing the unfired paste material and filling the insulating material is required, and the advantage of reducing the number of processes is reduced. In addition, it is necessary to prepare a solvent, a rinsing agent, or the like for removing the unfired paste material, resulting in an increase in manufacturing cost.

When the conventional direct wiring printing technique is applied to the formation of wiring patterns on a flexible substrate, there is a problem that cracks are generated between a solder resist and wiring when thermal cycle tests are performed on the obtained circuit board in and out of a low temperature environment and a high temperature environment.

Further, the colloidal silica used in the underlayer disclosed in patent document 4 has excellent adhesion to metal, but has poor adhesion to resin. Therefore, when the material of the base material is a resin, peeling may occur between the base layer and the base material, and reliability is low.

In the method described in patent document 5, an unfired paste material composed of cupric oxide (CuO) particles and a resin binder remains in a region not irradiated with laser light, the cupric oxide particles are large, the resin binder and the particles are locally present, and in this state, electrical insulation between wiring patterns is insufficient.

In the structure described in patent document 6, the wiring patterns are not filled, and in this state, electrical insulation between the wiring patterns cannot be ensured. In addition, in an environment with high humidity, air containing moisture enters between wiring patterns, and dielectric breakdown is likely to occur.

The present invention has been made in view of the above-described problems, and an object thereof is to provide a structure having conductive pattern regions, which can greatly simplify the manufacturing process, has excellent electrical insulation between the conductive pattern regions, and has excellent long-term reliability, and a method for manufacturing the structure.

In view of the above problems, an object of the present invention is to provide a laminate and a method for producing the laminate, which can reduce the production cost of a structure having a conductive pattern region without requiring equipment for realizing a vacuum atmosphere or an inert gas atmosphere in a photo-firing treatment of copper oxide.

Further, an object of the present invention is to provide a copper wiring capable of improving the conductivity of the wiring.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention.

That is, one embodiment of the structure of the present invention is characterized by comprising a support and a layer disposed on a surface constituted by the support, wherein the conductive pattern region containing copper and the insulating region containing copper oxide and phosphorus are adjacent to each other in the layer.

Another aspect of the structure of the present invention is characterized by comprising a support and a layer disposed on a surface constituted by the support, wherein the layer has a conductive pattern region containing copper and an insulating region containing copper oxide and hydrazine or hydrazine hydrate adjacent to each other.

Another aspect of the structure of the present invention is characterized by comprising a support and a layer disposed on a surface constituted by the support, wherein the layer has a conductive pattern region containing copper and an insulating region containing copper oxide, phosphorus and hydrazine or hydrazine hydrate adjacent to each other.

Another aspect of the structure of the present invention is characterized by comprising a support and a layer disposed on a surface constituted by the support, wherein the conductive pattern region containing copper and phosphorus and the insulating region containing copper oxide and phosphorus are adjacent to each other in the layer.

In addition, one embodiment of the laminate of the present invention is characterized by comprising a support, a coating layer containing copper oxide and phosphorus disposed on a surface constituted by the support, and a resin layer disposed so as to cover the coating layer.

In addition, one embodiment of the laminate of the present invention is characterized by comprising a support, a coating layer comprising copper oxide and hydrazine or hydrazine hydrate disposed on a surface constituted by the support, and a resin layer disposed so as to cover the coating layer.

In addition, one embodiment of the laminate of the present invention is characterized by comprising a support, a coating layer which is disposed on a surface constituted by the support and contains copper oxide, phosphorus, and contains hydrazine or hydrazine hydrate, and a resin layer disposed so as to cover the coating layer.

Further, one embodiment of the copper wiring of the present invention is a copper wiring containing reduced copper in which copper oxide is reduced, phosphorus and carbon, wherein an elemental concentration ratio of phosphorus to copper is 0.02 to 0.30, and an elemental concentration ratio of carbon to copper is 1.0 to 6.0.

In addition, one embodiment of the method for producing a structure according to the present invention is characterized by comprising the steps of: a step of disposing a coating layer containing copper oxide and a phosphorus-containing organic material on a surface constituted by a support; and a step of reducing the copper oxide to copper by selectively radiating light to the coating layer to obtain the support, and a layer in which an insulating region including the copper oxide and phosphorus and a conductive pattern region including the copper are disposed adjacent to each other on a surface constituted by the support.

In addition, one embodiment of the method for producing a structure according to the present invention is characterized by comprising the steps of: disposing a coating layer containing copper oxide, hydrazine or hydrazine hydrate on a surface constituted by a support; and a step of reducing the copper oxide to copper by selectively radiating light to the coating layer to obtain the support, and a layer in which an insulating region including the copper oxide and the hydrazine or hydrazine hydrate and a conductive pattern region including the copper are disposed adjacent to each other on a surface constituted by the support.

In addition, one embodiment of the method for producing a structure according to the present invention is characterized by comprising the steps of: disposing a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate on a surface constituted by a support; and a step of reducing the copper oxide to copper by selectively radiating light to the coating layer to obtain the support, and a layer in which an insulating region including the hydrazine or hydrazine hydrate and a conductive pattern region including the copper are disposed adjacent to each other on a surface constituted by the support, the insulating region including the copper oxide and the phosphorus.

In addition, one embodiment of the method for producing a laminate according to the present invention is characterized by comprising the steps of: a step of disposing a coating layer containing copper oxide and a phosphorus-containing organic material on a surface constituted by a support; and a step of disposing a resin layer so as to cover the coating layer.

In addition, one embodiment of the method for producing a laminate according to the present invention is characterized by comprising the steps of: disposing a coating layer containing copper oxide, hydrazine or hydrazine hydrate on a surface constituted by a support; and a step of disposing a resin layer so as to cover the coating layer.

In addition, one embodiment of the method for producing a laminate according to the present invention is characterized by comprising the steps of: disposing a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate on a surface constituted by a support; and a step of disposing a resin layer so as to cover the coating layer.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a structure having conductive pattern regions, which can greatly simplify the manufacturing process, is excellent in electrical insulation between the conductive pattern regions, and is excellent in long-term reliability, and a method for manufacturing the same.

Further, according to the present invention, it is possible to provide a laminate and a method for manufacturing the laminate, which can reduce the manufacturing cost of a structure having a conductive pattern region without requiring equipment for realizing a vacuum atmosphere or an inert gas atmosphere in the photo-firing treatment of copper oxide.

Further, according to the present invention, a copper wiring capable of improving the conductivity of the wiring can be provided.

Drawings

Fig. 1 is a schematic view showing a relationship between the cuprous oxide fine particles and the phosphate salt contained in the insulating region in the structure having the conductive pattern region according to the present embodiment.

Fig. 2 is a schematic cross-sectional view showing a structure having a conductive pattern region according to embodiment 1.

Fig. 3 is a schematic cross-sectional view showing a structure having a conductive pattern region according to embodiment 2.

Fig. 4 is a schematic cross-sectional view showing a structure having a conductive pattern region partially different from fig. 3.

Fig. 5 is a schematic cross-sectional view showing an example of a laminate according to the present embodiment.

Fig. 6 is a schematic cross-sectional view showing an example of a structure having a conductive pattern region manufactured using the laminate according to the present embodiment.

Fig. 7 is an explanatory diagram (an example) showing steps of the method for manufacturing a structure having a conductive pattern region according to embodiment 1.

Fig. 8 is an explanatory diagram (an example) showing steps of the method for manufacturing a structure having a conductive pattern region according to embodiment 2.

Fig. 9 is an electron micrograph for explaining a state of a crack in the coating layer of the example.

Fig. 10 is an electron micrograph for explaining a state of a crack in the coating layer of the example.

Fig. 11 is an electron micrograph showing a cross section of a layer formed on a support in the embodiment.

Fig. 12A is a photograph showing a conductive pattern region formed on a glass surface.

Fig. 12B is a schematic diagram of fig. 12A.

Fig. 12C is a photograph after removing the insulating region from fig. 12A.

Detailed Description

An embodiment of the present invention (hereinafter, simply referred to as "embodiment") will be described in detail.

< outline of Structure having conductive Pattern region (Structure having conductive Pattern region) >

The present inventors have found that, when a coating layer containing copper oxide is disposed on the surface of a support, and the coating layer is selectively irradiated with light, and copper oxide is reduced to copper to form conductive pattern regions, if the electrical insulation of the regions containing unreduced copper oxide is improved, insulation between the conductive pattern regions can be ensured without removing the regions and leaving them as they are, and a step of removing the regions is not required, and completed the present invention.

That is, the structure having the conductive pattern region according to the present embodiment is characterized in that phosphorus is contained in a coating layer containing copper oxide disposed on the surface of the support. Then, the coating layer is selectively irradiated with light to form conductive pattern regions, and insulating regions containing copper oxide and phosphorus are provided between the conductive pattern regions.

Fig. 1 is a schematic view showing a relationship between copper oxide fine particles and a phosphate salt contained in an insulating region in a structure having a conductive pattern region according to the present embodiment. As shown in fig. 1, in the insulating region 1, a phosphate 3, which is an example of a phosphorus-containing organic material, surrounds copper oxide particles 2, which is an example of copper oxide, such that phosphorus 3a faces inward and an ester 3b faces outward. Since the phosphate 3 exhibits electrical insulation, electrical conduction between adjacent copper oxide particles 2 is hindered.

Therefore, although the copper oxide fine particles 2 are semiconductor and conductive, they are covered with the phosphate 3 exhibiting electrical insulation. Thus, the insulating region 1 exhibits electrical insulation, and insulation between conductive pattern regions (described later) adjacent to both sides of the insulating region 1 can be ensured in a cross-sectional view (a cross-section along the up-down direction shown in fig. 2).

On the other hand, in the conductive pattern region, a part of the region of the coating layer containing copper oxide and phosphorus is irradiated with light, and copper oxide is reduced to copper in the part of the region. Copper obtained by reducing copper oxide in this manner is referred to as reduced copper. In addition, in this partial region, the phosphorus-containing organic matter is modified into phosphorus oxide. In the phosphorus oxide, the organic substance such as the ester salt 3b (see fig. 1) is decomposed by heat of laser light or the like, and does not exhibit electrical insulation.

In addition, as shown in fig. 1, when the copper oxide fine particles 2 are used, copper oxide is changed to reduced copper by heat of laser light or the like, and sintering is performed simultaneously, and the adjacent copper oxide fine particles 2 are integrated with each other. Thereby, a region having excellent electrical conductivity (hereinafter referred to as "conductive pattern region") can be formed.

In the conductive pattern region, phosphorus remains in the reduced copper. The phosphorus element is present in the form of at least 1 of elemental phosphorus, phosphorus oxide, and phosphorus-containing organic matter. The phosphorus element remained in this way is segregated in the conductive pattern region, and there is no concern that the resistance of the conductive pattern region is increased.

< constitution of structure having conductive pattern region: embodiment 1 ]

Fig. 2 is a schematic cross-sectional view showing a structure having a conductive pattern region according to embodiment 1. As shown in fig. 2, the structure 10 includes a support 11 and a layer 14 disposed on a surface formed by the support 11. In the layer 14, the insulating region 12 containing copper oxide and phosphorus and the conductive pattern region 13 containing copper are adjacent to each other. The copper herein is preferably the reduced copper described above. In addition, the phosphorus contained in the insulating region 12 is preferably contained in the form of a phosphorus-containing organic substance.

With this configuration, the conductive pattern regions containing copper can be insulated from each other by the insulating region containing copper oxide and phosphorus, and thus, it is not necessary to remove the unfired portion of the layer 14 for production. Therefore, the number of manufacturing steps can be reduced, and the manufacturing cost can be reduced because a solvent or the like is not required. In addition, the insulating region is used to insulate the conductive pattern region, and the insulating region is less likely to crack, thereby improving reliability.

Each constituent element of the structure having the conductive pattern region according to embodiment 1 will be described below.

< support body >

The support 11 constitutes a surface for disposing the layer 14. The shape is not particularly limited.

In order to ensure electrical insulation between the conductive pattern regions 13 separated by the insulating regions 12, the material of the support 11 is preferably an insulating material. Wherein the support 11 does not necessarily have to be entirely of an insulating material. Only the portion constituting the surface of the disposition layer 14 may be an insulating material.

The support 11 may more specifically be a flat plate-like body, a film or a sheet. The flat plate-like body is a support (also referred to as a base material) used for a circuit board such as a printed board. The film or sheet is, for example, a base film used as a film-like insulator for a flexible printed board.

The support 11 may be a solid object. The layer having the conductive pattern region may be arranged on a curved surface of the three-dimensional object or a surface including a broken slope, that is, a three-dimensional surface.

Examples of the three-dimensional object include housings of electrical devices such as mobile phone terminals, smart phones, smart glasses, televisions, and personal computers. Further, as another example of the three-dimensional object, a dash panel, an instrument panel, a steering wheel, a chassis, and the like are given in the automotive field.

The material of the stereoscopic substance is not limited, and for example, at least one selected from the group consisting of polypropylene resin, polyamide resin, acrylonitrile butadiene styrene resin, polyethylene resin, polycarbonate resin, polyacetal resin, polybutylene terephthalate resin, modified polyphenylene ether resin, and polyphenylene sulfide resin is preferable.

< layer (layer having conductive pattern region) disposed on surface of support >

In the present embodiment, the layer 14 is said to be formed by mixing the insulating region 12 and the conductive pattern region 13. Hereinafter, in the case of simply representing "layer", it is sometimes referred to as a layer having a conductive pattern region or a layer disposed on a support.

Layer 14 can be said to be an integral layer. In addition, the layer 14 may be said to be a single layer other than a multilayer structure. The term "integrated" and "unitary" refer to the insulating region 12 and the conductive pattern region 13 which are adjacent to each other in cross-section and are continuous along the surface. By "adjacent" is meant that no other layer is included between the insulating region 12 and the conductive pattern region 13. "continuous" refers to a state that does not include, for example, a state where a pattern between wiring layers is buried with a paste as one layer, which is observed in a printed board.

In the present embodiment, a broken slope may be generated between the surface of the insulating region 12 and the surface of the conductive pattern region 13. That is, the thickness becomes thin in the reduction process from copper oxide to copper, and thus there is a possibility that the film thickness of the conductive region and the insulating region may differ even in a continuous layer.

The insulating region 12 being adjacent to the conductive pattern region 13 means that electrical conductivity, particle state (fired and unfired), and the like may gradually change in the layer along the surface of the support, or a boundary (interface) may be present between the insulating region 12 and the conductive pattern region 13.

In addition, the insulating region 12 and the conductive pattern region 13 are formed of coating layers derived from the same composition. That is, since the conductive pattern region 13 is formed by irradiating a part of the coating layer with laser light, the insulating region 12 and the conductive pattern region 13 contain copper element, phosphorus element, and the like.

< insulating region >

The insulating region 12 contains copper oxide and phosphorus, and exhibits electrical insulation. The insulating region 12 can be said to be an unirradiated region which is not irradiated with light. The insulating region 12 can also be said to be an unreduced region where copper oxide is reduced without irradiation with light. The insulating region 12 may be an unfired region which is not fired by light irradiation.

< conductive Pattern area >

The conductive pattern region 13 contains copper, and exhibits electrical conductivity. The conductive pattern region 13 may be an irradiated region irradiated with light or a laser irradiated region. The conductive pattern region 13 may be said to be a reduction region containing reduced copper obtained by reducing copper oxide by irradiation with light. The conductive pattern region 13 may be a firing region including a fired body obtained by firing the insulating region 12 by light irradiation.

The shape of the conductive pattern region 13 in a plan view, that is, the pattern may be any of a straight line shape, a curved line shape, a round shape, a square shape, a curved shape, and the like, and is not particularly limited. The pattern is formed by light irradiation through a mask or by drawing by laser light, and is therefore not easily limited by shape.

The boundary between the insulating region 12 and the conductive pattern region 13 is preferably a straight line along the thickness direction (up-down direction shown in fig. 2) of the layer 14 in cross section view, but may have a taper angle, and is not particularly limited. Wherein the boundary does not have to be explicit. For example, when the composition ratio of copper is measured near the boundary, there may be a composition conversion region that gradually changes from the conductive pattern region 13 side to the insulating region 12 side.

The conductive pattern region 13 does not have to be completely reduced in cross-sectional view. For example, it is preferable that an unreduced portion exists near the portion of the support 11. This improves adhesion between the conductive pattern region 13 and the support 11.

As shown in fig. 2, in the present embodiment, the film thickness of the conductive pattern region 13 and the film thickness of the insulating region 12 may be different so that the film thickness of the insulating region 12 is thicker, for example. That is, in the reduction process of reducing copper from copper oxide to copper by laser irradiation, the film thickness of the conductive pattern region 13 is easily thinner than that of the insulating region 12. Since the film thicknesses are different, the creepage distance between the conductive pattern region 13 and the conductive pattern region 13 facing the insulating region 12 can be increased, and the insulating property can be improved. The thickness of the insulating region 12 is preferably 0.1 μm or more and 30 μm or less, more preferably 0.1 μm or more and 15 μm or less, and still more preferably 0.1 μm or more and 10 μm or less. In particular, when the film thickness is in the range of 1 μm to 10 μm, the insulating property as the insulating region 12 can be maintained, and the conductive pattern region 13 having more excellent adhesion to a substrate and conductivity can be produced by light irradiation described later, which is preferable. The film thickness of the conductive pattern region 13 is preferably 10% to 90%, more preferably 20% to 80%, and even more preferably 30% to 70% with respect to the film thickness of the insulating region 12. In particular, when the content is 30% to 70%, the adhesion of the base material can be maintained, and electrical conductivity sufficient for use as an electrical wiring can be obtained, which is preferable.

< sealing layer >

An adhesive layer (not shown) is preferably provided between the support 11 and the layer 14 having the conductive pattern region. The adhesion of the layer 14 to the support 11 can be improved by the adhesion layer, and peeling of the insulating region 12 and the conductive pattern region 13 can be prevented, thereby improving the long-term stability of the structure 10.

The adhesive layer includes, for example, (i) a layer obtained by roughening the surface constituted by the support 11, and (ii) a layer obtained by disposing a coating layer on the surface constituted by the support 11. An example of (i) is a part of the support 11 itself. In this case, other layers (e.g., primer (base) layer) may be combined with the sealing layer.

In the case of (ii), the sealing layer may be a single coating layer or may be laminated with other layers. In addition, the coating layer may include a primer material.

< detailed description of Structure having conductive Pattern region >

The following further describes the respective configurations of the structure 10 according to the present embodiment. However, the respective configurations are not limited to the specific examples described below.

(support)

Specific examples of the support include a support made of an inorganic material (hereinafter referred to as an "inorganic support") and a support made of a resin (hereinafter referred to as a "resin support").

The inorganic support is composed of, for example, glass, silicone, mica, sapphire, crystal, clay film, ceramic material, or the like. Ceramic materials are, for example, aluminum oxide, silicon nitride, silicon carbide, zirconium oxide, yttrium oxide and aluminum nitride, and mixtures of at least 2 of these. As the inorganic support, a support made of glass, sapphire, crystal, or the like having high light transmittance can be used in particular.

As the resin support, for example, a resin support made of polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), ethylene (PS), styrene-butadiene copolymer, polyethylene-vinyl fluoride (PE), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), polyetheretherketone (PVDF) and (PVDF) may be used, A support made of polyvinyl phenol, polychloroprene, polyoxymethylene, polysulfone (PSF), polyphenylsulfone resin (PPSU), cyclic Olefin Polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), nylon resin (PA 6, PA 66), polybutylene terephthalate resin (PBT), polyethersulfone resin (PESU), polytetrafluoroethylene resin (PTFE), polytrifluoroethylene (PCTFE), silicone resin, or the like.

In addition, although not distinguished above, a resin sheet containing cellulose nanofibers may be used as a support.

In particular, at least one selected from the group consisting of PI, PET, and PEN has excellent adhesion to a layer having a conductive pattern region and an adhesion layer, and is excellent in market flow and available at low cost, and is significant and preferable from an industrial point of view.

In addition, in particular, in the case of the case, at least one selected from the group consisting of PP, PA, ABS, PE, PC, POM, PBT, m-PPE and PPS is excellent in adhesion to the layer having the conductive pattern region and the adhesion layer, and in moldability and mechanical strength after molding. Further, they are preferable because they have heat resistance that is sufficiently resistant to laser irradiation and the like at the time of forming the conductive pattern region.

The load deformation temperature of the resin support is preferably 400 ℃ or less, more preferably 280 ℃ or less, and even more preferably 250 ℃ or less. A support having a load deformation temperature of 400 ℃ or less can be obtained at low cost, and is significant and preferable from an industrial point of view. The load deformation temperature is measured, for example, in accordance with JIS K7191.

The thickness of the support may be, for example, 1 μm to 100mm, preferably 25 μm to 10mm, more preferably 25 μm to 250 μm. When the thickness of the support is 250 μm or less, the fabricated electronic device can be made light, space-saving and flexible, and thus is preferable.

In the case where the support is a case, the thickness thereof may be, for example, 1 μm to 1000mm, preferably 200 μm to 100mm, and 200 μm to 5mm. The present inventors have clarified that by selecting the thickness in this range, mechanical strength and heat resistance after molding can be exhibited.

When the support or the support has an adhesive layer, the support containing the adhesive layer preferably has a light transmittance of 30% or more, more preferably 40% or more, and still more preferably 50% or more, with respect to a light having a wavelength of 445 nm. The upper limit of the light transmittance may be 98% or less. Regarding the wavelength, wavelengths from near ultraviolet to near infrared such as 355nm, 405nm, 450nm, 532nm, 1064nm, etc. may be selected in addition to 445 nm. By increasing the light transmittance at such a wavelength, the coated layer can be fired by irradiation with light from the support side, thereby forming a layer having a conductive pattern region.

(layer having conductive pattern region) disposed on surface of support)

The layer is formed by an insulating region comprising copper oxide and a phosphorus-containing organic material adjacent to a conductive pattern region comprising copper.

(copper oxide)

In this embodiment, the copper oxide includes, for example, cuprous oxide and cupric oxide (CuO). Cuprous oxide tends to be easily sintered at low temperature, and is particularly preferable. The cuprous oxide and cupric oxide may be used alone or in combination.

The copper oxide fine particles have a core/shell structure, and either the core or the shell may be cuprous oxide or may contain cupric oxide.

The copper oxide contained in the insulating region is formed into a particulate shape, for example. The average particle diameter of the fine particles containing copper oxide is 1nm to 100nm, more preferably 1nm to 50nm, still more preferably 1nm to 20 nm. The smaller the particle diameter, the more excellent the electrical insulation of the insulating region, and thus preferable.

Copper particles may be included in the insulating region. That is, copper may be added to the dispersion described later. The phosphorus-containing organic matter is also adsorbed on the surface of the copper particles, and electrical insulation can be exhibited.

(phosphorus-containing organic matter)

The phosphorus contained in the insulating region is preferably a phosphorus-containing organic substance. The phosphorus-containing organic material is a material exhibiting electrical insulation in the insulating region. The phosphorus-containing organic material is preferably capable of fixing copper oxide to a support or an adhesive layer. The phosphorus-containing organic substance may be a single molecule or a mixture of two or more molecules. In addition, the phosphorus-containing organic matter may be adsorbed on the fine particles of copper oxide.

The number average molecular weight of the phosphorus-containing organic compound is not particularly limited, and is preferably 300 to 300,000. When the molecular weight is 300 or more, electrical insulation is excellent.

The phosphorus-containing organic substance is preferably readily decomposed or evaporated under the action of light or heat. By using an organic substance which is easily decomposed or evaporated by light or heat, a conductive pattern region having a low resistivity can be obtained without easily leaving residues of the organic substance after firing.

The decomposition temperature of the phosphorus-containing organic substance is not limited, but is preferably 600 ℃ or lower, more preferably 400 ℃ or lower, and further preferably 200 ℃ or lower. The boiling point of the phosphorus-containing organic substance is not limited, but is preferably 300℃or lower, more preferably 200℃or lower, and further preferably 150℃or lower.

The absorption characteristics of the phosphor-containing organic material are not limited, and light used for firing is preferably absorbed. For example, when a laser is used as a light source for firing, a phosphor-containing organic material that absorbs light having an emission wavelength (center wavelength) of 355nm, 405nm, 445nm, 450nm, 532nm, 1064nm, for example, is preferably used. In the case where the support is a resin, wavelengths of 355nm, 405nm, 445nm, and 450nm are particularly preferable.

Further, the structure may be a phosphate ester salt of a high molecular weight copolymer having a group having affinity with copper oxide. For example, the structure of chemical formula (1) is preferable because copper oxide can be adsorbed and adhesion to a support is excellent.

[ chemical 1]

Chemical formula (1)

In the chemical formula (1), R is an ester salt.

An example of the ester salt is represented by the formula (2).

[ chemical 2]

Chemical formula (2)

Further, as an example of the phosphorus-containing organic material, the structure of chemical formula (3) can be given.

[ chemical 3]

Chemical formula (3)

In the chemical formula (3), l is an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10, m is an integer of 1 to 2, preferably an integer of 1 to 15, more preferably an integer of 1 to 10, and n is an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10.

Examples of the organic structure of the phosphorus-containing organic substance include polyethylene glycol (PEG), polypropylene glycol (PPG), polyimide, polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyarylate (PAR), polyamide (PA), polyamide imide (PAI), polyether imide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polyethylene copolymer (PS), styrene-butene-diene copolymer, poly (PE), polyvinylbutyral (PE), vinyltoluene, polyvinylbutyral (PVDF), vinyltoluene (PVDF), and vinyltoluene (PVDF, polyoxymethylene, polysulfone (PSF), polysulfide, silicone resin, aldehyde sugar, cellulose, amylose, pullulan, dextrin, dextran, fructose, chitin, and the like. The functional groups of these structures may be modified, modified structures may be used, or copolymers of these structures may be used. The phosphorus-containing organic material having a skeleton selected from the group consisting of a polyethylene glycol structure, a polypropylene glycol structure, a polyacetal structure, a polybutene structure and a polysulfide structure is preferably because it is easy to decompose and residue is not easy to remain in the conductive pattern region obtained after firing.

As a specific example of the phosphorus-containing organic material, a commercially available material, specifically, examples of the materials include DISPERBYK (registered trademark) -102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-140, DISPERBYK-145, DISPERBYK-168, DISPERBYK-180, DISPEYK-182, DISPEYK-187, DISPEYK-190, DISPEYK-191, DISPEYK-193, DISPEYK-194N, DISPERBYK-199, DISPEYK-2000, DISPEYK-2001, DISPEYK-2008, DISPEYK-2009 DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2013, DISPERBYK-2015, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2152, DISPERBYK-2055, DISPERBYK-2060, DISPERBYK-2061, DISPERBYK-2164, DISPERBYK-2096, DISPERBYK-2200, BYK (registered trademark) -405, BYK-607, BYK-9076, BYK-9077, BYK-P105, plysurf DBS manufactured by first Industrial pharmaceutical company, and the like. These may be used alone or in combination of two or more.

In the insulating region, fine particles containing copper oxide (hereinafter referred to as "copper oxide fine particles") are mixed with a phosphorus-containing organic substance, and the content of the phosphorus-containing organic substance may be 5 parts by volume or more and 900 parts by volume or less, assuming that the total volume of the copper oxide fine particles is 100 parts by volume. The lower limit is preferably 10 parts by volume or more, more preferably 30 parts by volume or more, and still more preferably 60 parts by volume or more. The upper limit is preferably 480 parts by volume or less, more preferably 240 parts by volume or less.

The content of the phosphorus-containing organic substance is preferably 1 part by weight or more and 150 parts by weight or less per 100 parts by weight of the copper oxide fine particles. The lower limit is preferably 2 parts by weight or more, more preferably 5 parts by weight or more, and still more preferably 10 parts by weight or more. The upper limit is preferably 80 parts by weight or less, more preferably 40 parts by weight or less.

When the content of the phosphorus-containing organic substance relative to the copper oxide fine particles is 5 parts by volume or more or 1 part by weight or more, a film having a submicron thickness can be formed. When the content of the phosphorus-containing organic material is 10 parts by volume or more or 5 parts by weight or more, a thick film having a thickness of several tens micrometers can be formed as a layer. When the content of the phosphorus-containing organic compound is 30 parts by volume or more or 10 parts by weight or more, a layer having high flexibility and being less likely to crack even when bent can be obtained.

When the content of the phosphorus-containing organic substance relative to the copper oxide fine particles is 900 parts by volume or less or 150 parts by weight or less, a good conductive pattern region can be obtained by firing.

(hydrazine or hydrazine hydrate)

Hydrazine or hydrazine hydrate may be contained in the coating layer or may remain in the insulating region as an unfired region. By containing hydrazine or hydrazine hydrate, the dispersion stability of copper oxide is further improved and the reduction of copper oxide during firing is facilitated, and the resistance of the conductive film is further reduced. The hydrazine content is preferably the following.

0.0001 + (hydrazine mass/copper oxide mass) +.0.10 (1)

Regarding the content of the reducing agent, when the mass ratio of hydrazine is 0.0001 or more, the resistance of the copper film decreases. In addition, when the mass ratio is 0.1 or less, the long-term stability of the copper oxide ink is improved, and thus it is preferable.

(mass ratio of copper particles/copper oxide particles in insulating region)

The insulating region may contain copper particles in addition to the copper oxide particles. In this case, the mass ratio of the copper particles to the copper oxide fine particles (hereinafter referred to as "copper particles/copper oxide fine particles") is preferably 1.0 to 7.0.

The copper particles/copper oxide fine particles are preferably 1.0 to 7.0 in terms of conductivity and crack prevention.

(average particle diameter in copper oxide particles)

The average secondary particle diameter of the copper oxide fine particles is not particularly limited, but is preferably 500nm or less, more preferably 200nm or less, and further preferably 80nm or less. The average secondary particle diameter of the fine particles is preferably 5nm or more, more preferably 10nm or more, and even more preferably 15nm or more.

The average secondary particle diameter is the average particle diameter of an aggregate (secondary particle) formed by aggregation of a plurality of primary particles. When the average secondary particle diameter is 500nm or less, a fine conductive pattern region tends to be easily formed on the support, which is preferable. When the average secondary particle diameter is 5nm or more, the long-term storage stability of the dispersion is improved, and thus it is preferable. The average secondary particle diameter of the fine particles can be measured by, for example, a transmission electron microscope or a scanning electron microscope.

The average primary particle diameter of primary particles constituting the secondary particles is preferably 100nm or less, more preferably 50nm or less, and still more preferably 20nm or less. The average primary particle diameter is preferably 1nm or more, more preferably 2nm or more, and still more preferably 5nm or more.

When the average primary particle diameter is 100nm or less, the firing temperature to be described later tends to be lowered. The reason why such low-temperature firing is possible is considered to be that the smaller the particle diameter of the particles is, the larger the surface energy is and the lower the melting point is.

In addition, when the average primary particle diameter is 1nm or more, good dispersibility can be obtained, and thus it is preferable. In the case of forming a wiring pattern on the support, the average primary particle diameter is preferably 2nm to 100nm, more preferably 5nm to 50nm, from the viewpoints of adhesion to the substrate and reduction in resistance. This tendency is remarkable when the substrate is a resin. The average primary particle diameter of the fine particles can be measured by a transmission electron microscope or a scanning electron microscope.

The content of the copper oxide fine particles in the layer disposed on the support is preferably 40 mass% or more, more preferably 55 mass% or more, and still more preferably 70 mass% or more, per unit mass of the region including copper oxide and the phosphorus-containing organic material. The content is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

The content of the copper oxide fine particles in the layer disposed on the support is preferably 10% by volume or more, more preferably 15% by volume or more, and still more preferably 25% by volume or more, per unit volume. The content is preferably 90% by volume or less, more preferably 76% by volume or less, and still more preferably 60% by volume or less.

When the content of the copper oxide fine particles in the insulating region is 40% by mass or more or 10% by volume or more, the fine particles are fused to each other by firing to exhibit conductivity, and it is preferable that the higher the concentration is, the higher the conductivity is obtained. When the content is 98% by mass or less or 90% by volume, the layer disposed on the support can be attached as a film to the support or the adhesive layer, which is preferable. When the content is 95% by mass or less or 76% by volume, the adhesive layer can be more strongly adhered to the support or the adhesive layer, which is preferable. When the content is 90% by mass or less or 60% by volume, the flexibility of the layer is increased, cracking is less likely to occur at the time of bending, and the reliability is high. Further, when the content of the copper oxide fine particles in the insulating region is 90% by volume or more, the insulating resistance value of the insulating region is reduced, and the insulating property is excellent, which is preferable. Copper oxide includes cuprous oxide (Cu ₂ O) and cupric oxide (CuO), cuprous oxide is preferable from the viewpoints of low resistance and absorbance.

The copper oxide contained in the insulating region in this embodiment mode can be commercially available or a composite can be used. As a commercial product, for example, there may be mentioned cuprous oxide fine particles having an average primary particle diameter of 18nm sold by EM Japan company.

Examples of the synthesis method of the fine particles containing cuprous oxide include the following methods.

(1) Adding water and a copper acetylacetonate complex to a polyhydric alcohol solvent, heating and dissolving an organic copper compound temporarily, adding water in an amount required for the reaction, and heating to a reduction temperature of the organic copper for reduction.

(2) A method in which an organocopper compound (copper-N-nitrosophenyl hydroxylamine complex) is heated at a high temperature of about 300 ℃ in the presence of a protective agent such as hexadecylamine in an inert atmosphere.

(3) A method for reducing copper salts dissolved in an aqueous solution with hydrazine.

The method (1) can be carried out under the conditions described in, for example, angewandte Chemi International Edition, volume 40, volume 2, p.359, 2001.

The method (2) can be carried out under the conditions described in, for example, journal of American Chemical Society,1999, volume 121, p.11595.

In the method of the above (3), as the copper salt, a binary copper salt may be suitably used, and examples thereof include copper (II) acetate, copper (II) nitrate, copper (II) carbonate, copper (II) chloride, copper (II) sulfate, and the like. The amount of hydrazine to be used is preferably 0.2 to 2 moles, more preferably 0.25 to 1.5 moles, relative to 1 mole of the copper salt.

The water-soluble organic substance may be added to the aqueous solution in which the copper salt is dissolved. By adding a water-soluble organic substance to the aqueous solution, the melting point of the aqueous solution is reduced, and therefore, the reduction can be performed at a lower temperature. Examples of the water-soluble organic substance include alcohols and water-soluble polymers.

As the alcohol, for example, methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, ethylene glycol, propylene glycol, glycerin, and the like can be used. Examples of the water-soluble polymer include polyethylene glycol, polypropylene glycol, and polyethylene-polypropylene glycol copolymer.

In the method (3), the temperature at the time of reduction may be, for example, -20 to 60℃and preferably-10 to 30 ℃. The reduction temperature may be constant during the reaction, or may be increased or decreased in the middle. The reduction is preferably performed at 10℃or less, more preferably at 0℃or less, at the beginning of the reaction where the activity of hydrazine is high. The reduction time is preferably 30 minutes to 300 minutes, more preferably 90 minutes to 200 minutes. The atmosphere at the time of reduction is preferably an inert atmosphere such as nitrogen or argon.

Among the above methods (1) to (3), the method (3) is preferred because it is simple to handle and can give particles having a small particle diameter.

In the above-described embodiment, the insulating region includes copper oxide and phosphorus. In contrast, as another embodiment, a method in which copper oxide and hydrazine or hydrazine hydrate are contained in the insulating region, or a method in which copper oxide, hydrazine or hydrazine hydrate and phosphorus are contained in the insulating region can be shown. That is, the layer is composed of a conductive pattern region containing copper and an insulating region containing copper oxide and hydrazine or hydrazine hydrate adjacent to each other. Alternatively, the layer may be formed such that a conductive pattern region containing copper and an insulating region containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus are adjacent to each other; or a conductive pattern region containing copper and phosphorus and an insulating region containing copper oxide, hydrazine or hydrazine hydrate, and phosphorus are formed adjacent to each other.

Thus, in this embodiment, hydrazine or hydrazine hydrate may be contained in the insulating region. By including hydrazine or hydrazine hydrate in the coating layer, copper oxide is easily reduced to copper after exposure to light. By including hydrazine or hydrazine hydrate, the reduced copper can be reduced in resistance. Hydrazine or hydrazine hydrate remains in the insulating region which is not irradiated with light.

(conductive pattern region)

The copper in the conductive pattern region may, for example, exhibit a structure in which particles containing copper are welded to each other. The shape of the particles may be particle-free, and the whole particles may be fused. The shape of the particles may be partially changed, and a state in which most of the particles are fused may be adopted. As described above, the copper is preferably reduced copper. The conductive pattern region preferably includes a fired body obtained by firing the insulating region. Thereby, the conductivity of the conductive pattern region can be improved. Further, since the conductive pattern region can be formed by firing the insulating region, the conductive pattern region can be easily formed, and the "layer" in the present embodiment in which the conductive pattern region and the insulating region are mixed can be formed with high accuracy.

The conductive pattern region may contain at least one of copper oxide (cuprous oxide, cupric oxide, monovalent copper oxide), phosphorus element, phosphorus oxide, and phosphorus-containing organic substance, in addition to copper. For example, the surface side portion of the conductive pattern region may be formed by welding fine particles containing copper to each other, and the support side portion may be formed by containing copper oxide or a phosphorus-containing organic material. Thus, copper oxide or a phosphorus-containing organic substance can cause firm bonding of copper particles to each other, and further, copper oxide or a phosphorus-containing organic substance can improve adhesion to a support or an adhesion layer, which is preferable.

The element concentration ratio of phosphorus/copper in the conductive pattern region is preferably 0.02 to 0.30, more preferably 0.05 to 0.28, and still more preferably 0.1 to 0.25. The element concentration ratio of phosphorus to copper is preferably 0.02 or more, whereby oxidation of copper can be suppressed, and reliability as a copper wiring circuit can be improved. Further, it is preferable that the element concentration ratio of phosphorus to copper is 0.30 or less, so that the resistance value of the conductive pattern region can be reduced.

As described above, the layer in this embodiment may be configured such that the conductive pattern region containing copper and phosphorus and the insulating region containing copper oxide and phosphorus are adjacent to each other. This can improve both the conductivity in the conductive pattern region and the insulation in the insulation region. It is believed that in the conductive pattern region, since oxidation of phosphorus occurs before copper is oxidized in the manufacturing process, the resistance change of the conductive pattern region can be suppressed to be low.

The content of copper in the conductive pattern region is preferably 50% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, and may be 100% by volume. The copper content is preferably 50 vol% or more, since the electrical conductivity is improved.

The surface of the conductive pattern region, which is in contact with a resin layer described later, may have a roughness equal to or greater than a predetermined level. Specifically, the surface roughness Ra is preferably 20nm to 500nm, more preferably 50nm to 300nm, and still more preferably 50nm to 200 nm. When the roughness is within this range, a part of the resin layer is preferably made to intrude into the concave-convex portion on the surface of the conductive pattern region, so that the adhesion can be improved.

(sealing layer)

In the structure with a wiring pattern region according to the present embodiment, it is preferable that an adhesive layer is provided between the support and the layer having the conductive pattern region. That is, it is preferable that the support has an adhesive layer on a surface thereof, and a layer having a conductive pattern region is disposed on a surface thereof.

The surface of the support is preferably roughened by an adhesive layer.

By roughening the surface of the support, copper oxide and a phosphorus-containing organic substance in the layer disposed on the surface of the support can be firmly bonded to the surface of the support.

The sealing layer can be formed by roughening the surface of the support by rough polishing, sandblasting, chemical etching, reactive ion etching, plasma treatment, sputtering, UV ozone treatment, or the like. The adhesive layer may be formed by roughening the surface of a surface formed by applying a coating material to a support. The mode may be appropriately selected depending on the material of the support.

(coating Material)

Examples of the coating material include an organic material, an inorganic material, and an organic-inorganic composite material.

The coating material preferably has a bonding structure. Examples of the binding structure include a hydroxyl group (-OH group), an amino group, a mercapto group, a phosphate group, a phosphonate group, a functional group having a succinimide skeleton, a functional group having a pyrrolidone skeleton, a selenol group, a polysulfide group, a polyselenide group, a carboxyl group, a functional group having an acid anhydride skeleton, a sulfonic acid group, a nitro group, a cyano group, an isocyanate group, an azide group, a silanol group, a silyl ether group, and a hydrosilyl group. The binding structure is preferably at least one selected from the group consisting of a hydroxyl group (—oh group), an amino group, a phosphonic acid group, and a carboxylic acid group. the-OH groups are more preferably Ar-OH groups (Ar means aromatic) and/or Si-OH groups.

When the coating material has an Ar-O structure (Ar means aromatic) and/or an Si-O structure, it is also preferable in view of adhesion.

The coating material may be an organic material shown in the following chemical formula group.

[ chemical 4]

Chemical formula (4)

In the chemical formula group, n is an integer more than 1, X is a main skeleton of an organic material, and R is a functional group. Examples of the functional group represented by R in the above formula group include hydrogen, halogen, alkyl (for example, methyl, isopropyl, tert-butyl, etc.), aryl (for example, phenyl, naphthyl, thienyl, etc.), haloaryl (for example, pentafluorophenyl, 3-fluorophenyl, 3,4, 5-trifluorophenyl, etc.), alkenyl, alkynyl, amido, acyl, alkoxy (for example, methoxy, etc.), aryloxy (for example, phenoxy, naphthyl, etc.), haloalkyl (for example, perfluoroalkyl, etc.), thiocyano, hydroxyl, amino, mercapto, phosphonic acid, phosphonate, a functional group having a succinimide skeleton, a functional group having a pyrrolidone skeleton, seleno, polysulfide, polyselenide, carboxylic acid, a functional group having an anhydride skeleton, sulfonic acid, nitro, cyano, and a combination thereof. When the adhesive layer contains an organic material having such a bonding structure, the adhesive property between the support and the layer having the conductive pattern region tends to be good.

As the organic material, an organic material having an aromatic structure (Ar) can be suitably used. Since the organic material having an aromatic structure has a high softening temperature and decomposition temperature, deformation of the support during firing can be suppressed, and the layer having the conductive pattern region disposed on the support is less likely to be broken by the decomposition gas of the support. Thus, a conductive film with low resistance can be obtained by firing. As the aromatic structure, aromatic hydrocarbons such as benzene, naphthalene, anthracene, naphthacene, pentacene, phenanthrene, pyrene, perylene, benzo [9,10] phenanthrene, and the like can be used; and heteroaromatic compounds such as thiophene, thiazole, pyrrole, furan, pyridine, pyrazole, imidazole, pyridazine, pyrimidine, and pyrazine. The number of electrons included in the pi-electron system of the aromatic structure is preferably 22 or less, more preferably 14 or less, and further preferably 10 or less. When the number of electrons included in the pi-electron system is 22 or less, crystallinity does not become excessively high, and a soft and smooth adhesive layer can be obtained. In these aromatic structures, a part of hydrogen bonded to an aromatic ring may be substituted with a functional group. Examples of the functional group include halogen, alkyl (e.g., methyl, isopropyl, and t-butyl), aryl (e.g., phenyl, naphthyl, and thienyl), halogenated aryl (e.g., pentafluorophenyl, 3-fluorophenyl, and 3,4, 5-trifluorophenyl), alkenyl, alkynyl, amide, acyl, alkoxy (e.g., methoxy), aryloxy (e.g., phenoxy, and naphthyl), haloalkyl (e.g., perfluoroalkyl), thiocyano, and hydroxyl. The organic material preferably has an aromatic hydroxyl group (Ar-OH group), and particularly preferably a phenolic hydroxyl group (Ph-OH group). In addition, an organic material having an ar—o structure in which oxygen having an aromatic hydroxyl group is bonded to other structures tends to be less likely to decompose during firing, and is therefore preferable.

Examples of the organic material include polyimide, polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal, polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyether imide (PEI), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ketone (PEK), polyphthalamide (PPA), polyether nitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide, nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, polychloroprene, ethylene-propylene-diene copolymer, nitrile rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, urethane rubber, butyl rubber, fluororubber, polymethylpentene (pp), styrene-butadiene), styrene-acrylonitrile copolymer (PE), polyvinyl chloride, polyvinylidene fluoride (PVDF), polyvinyl chloride (PE), polyvinyl chloride (PVDF), and polyvinyl chloride (PVDF Polyvinylphenol, polychloroprene, polyoxymethylene, polysulfone (PSF), silicone resins, and the like. The organic material is preferably at least one selected from the group consisting of phenol resin, novolac, polyvinyl phenol, and polyimide.

Examples of the inorganic material include metals, alloys, metal oxides, metal nitrides, metal carbides, metal oxycarbides, and metal fluorides. As the inorganic material, in particular, examples of the metal oxide include silicon oxide, silver oxide, copper oxide, aluminum oxide, zirconium oxide, titanium oxide, hafnium oxide, tantalum oxide, tin oxide, calcium oxide, cerium oxide, chromium oxide, cobalt oxide, holmium oxide, lanthanum oxide, magnesium oxide, manganese oxide, molybdenum oxide, nickel oxide, antimony oxide, samarium oxide, terbium oxide, tungsten oxide, yttrium oxide, zinc oxide, indium Tin Oxide (ITO), silver fluoride, silicon fluoride, aluminum fluoride, zirconium fluoride, titanium fluoride, hafnium fluoride, tantalum fluoride, tin fluoride, calcium fluoride, cerium fluoride, cobalt fluoride, holmium fluoride, lanthanum fluoride magnesium fluoride, manganese fluoride, molybdenum fluoride, nickel fluoride, antimony fluoride, samarium fluoride, terbium fluoride, tungsten fluoride, yttrium fluoride, zinc fluoride, lithium fluoride, lead zirconate titanate (PZT), barium titanate, strontium titanate, copper nitride, silicon nitride, aluminum nitride, titanium nitride, hafnium nitride, tantalum nitride, tin nitride, calcium nitride, cerium nitride, cobalt nitride, holmium nitride, lanthanum nitride, magnesium nitride, manganese nitride, molybdenum nitride, nickel nitride, antimony nitride, samarium nitride, terbium nitride, tungsten nitride, yttrium nitride, zinc nitride, lithium nitride, gallium nitride, siC, siCN, diamond-like carbon (DLC), and the like. The inorganic material having a hydroxyl group is preferable because it has excellent adhesion to the support and the layer having the conductive pattern region. In particular, hydroxyl groups are present on the surface of the metal oxide, and thus the metal oxide is preferable. Among the metal oxides, particularly, an inorganic material having a si—o structure is more preferable.

The inorganic material is more specifically preferably at least 1 selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, indium tin oxide, and aluminum oxide. Silica and alumina are particularly preferred.

The adhesive layer preferably contains fine particles having a particle diameter of 10nm to 500 nm. Specifically, the adhesion layer preferably contains fine particles of silica or alumina having a particle diameter of 10nm to 500 nm. This can increase the specific surface area after the formation of the layer having the conductive pattern region, and can improve adhesion with the layer having the conductive pattern region. The fine particles may be porous particles.

As the inorganic material, an inorganic semiconductor can also be used. Examples of the inorganic semiconductor material include elemental semiconductor, oxide semiconductor, compound semiconductor, sulfide semiconductor, and the like. As the elemental semiconductor, silicon and germanium can be exemplified, for example. Examples of the oxide semiconductor include IGZO (indium-gallium-zinc oxide), IZO (indium-zinc oxide), zinc oxide, indium oxide, titanium oxide, tin oxide, tungsten oxide, niobium oxide, and cuprous oxide. Examples of the compound semiconductor include gallium arsenide (GaAs), gallium arsenide phosphide (GaAsP), gallium phosphide (GaP), cadmium selenide (CdSe), silicon carbide (SiC), indium antimonide (InSb), and gallium nitride. As the sulfide semiconductor, molybdenum sulfide, cadmium sulfide, and the like can be exemplified.

As the organic-inorganic composite material, for example, an organic material in which inorganic fine particles are dispersed and an organometallic compound can be used. As the inorganic fine particles, particles of the above inorganic material can be used. Examples of the organometallic compound include silicate, titanate, and aluminate. As the silicate ester, methyl silicate, ethyl silicate, and the like can be used.

The thickness of the sealing layer is preferably 20 μm or less. Thus, the support body can be prevented from being warped. The film thickness of the adhesive layer is more preferably 10 μm or less, still more preferably 1 μm or less, and from the viewpoint of adhesion, it is preferably 0.01 μm or more, still more preferably 0.05 μm or more, still more preferably 0.1 μm or more.

(primer coating material)

The sealing layer may be formed of a single material, or may be formed by mixing or laminating two or more materials. For example, the sealing layer may comprise a primer material. In addition, for example, a layer formed of a primer material may be disposed between the support and the layer formed of the coating material, or between the layer formed of the coating material and the layer having the conductive pattern region.

When the adhesion layer includes a layer made of a primer material, the adhesion tends to be further improved. The layer composed of the primer material may be formed by, for example, a primer treatment of forming a thin layer of the primer material on the surface.

The primer material preferably has a bonding structure. The bonding structure described in the item "(coating material)" is exemplified as the bonding structure. By providing the primer material with a bonding structure, the bonding structure is introduced into the adhesive layer, and thus high adhesion tends to be obtained.

The adhesive layer may be formed by disposing a layer made of a coating material on the support after the primer treatment. Alternatively, a layer made of a coating material may be disposed on the support, and then the layer may be subjected to a primer treatment to form an adhesive layer. Alternatively, the adhesive layer may be formed by pre-mixing the coating material and the primer material and then disposing the mixture on the support, or the adhesive layer may be formed by disposing a layer made of the primer material on the support. When the primer treatment is performed on the layer made of the coating material, the density of the bonding structure on the surface can be increased, and thus higher adhesion can be obtained.

Examples of the primer material include a silane coupling agent, a phosphonic acid-based low-molecular material, and a thiol-based material.

Examples of the silane coupling agent include compounds having a functional group such as a vinyl group, an amino group, an epoxy group, a styryl group, a methacryloyl group, an acryl group, an isocyanurate group, an ureido group, a mercapto group, an isocyanate group, and a phosphonic acid group at the terminal. Specific examples of the silane coupling agent include vinylmethoxysilane, vinylethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylideneamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyl-methoxysilyl, and mercapto-3-glycidoxypropylsilyl salts thereof, 3-mercaptopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane.

Examples of the phosphonic acid-based material include compounds having a functional group such as a vinyl group, an amino group, an epoxy group, a styryl group, a methacryloyl group, an acryl group, an isocyanurate group, a urea group, a mercapto group, an isocyanate group, a silyl group, a silanol group, or a silyl ether group at the terminal. Specific examples of the phosphonic acid-based material include aminomethylphosphonic acid, 2-aminoethylphosphonic acid, O-phosphorylethanolamine, 12-aminododecylphosphonic acid, 12-aminoundecylphosphonate, 6-aminohexylphosphonic acid, 6-aminohexylphosphonate, 12-azidodecylphosphonic acid, (12-dodecylphosphonic acid) N, N-dimethyl-N-octadecylammonium bromide, (12-dodecylphosphonic acid) N, N-dimethyl-N-octadecyl ammonium chloride, (12-dodecylphosphonic acid) pyridinium bromide, (12-dodecylphosphonic acid) triethylammonium chloride, 11-hydroxyundecylphosphonic acid, 12-mercaptododecylphosphonic acid, 11-mercaptoundecylphosphonic acid, 11-methacryloxyundecylphosphonic acid, 4-nitrobenzylphosphonic acid, 12-phosphono-1-dodecylsulfonic acid, (6-phosphonohexyl) phosphonic acid, 11-phosphonoundecanoic acid, 11-phosphonoundecylacrylate, propylene diphosphonic acid, 4-aminobenzyl phosphonic acid, 1, 8-octanediphosphonic acid, 1, 10-decyldiphosphonic acid, 6-phosphonohexanoic acid, (1-amino-2-methylpropyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (3-nitrophenyl) phosphonic acid, 1-hydroxyethane-1, bisphosphonic acids, 3-aminopropylphosphonic acid, 4-aminobutylphosphonic acid, nitrilotris (methylene) triphosphonic acid, methylenediphosphonic acid, and the like.

As the thiol material, for example, a compound having a functional group such as a vinyl group, an amino group, an epoxy group, a styryl group, a methacryloyl group, an acryl group, an isocyanurate group, a urea group, an isocyanate group, a silyl group, a silanol group, a silyl ether group, or a phosphonic acid group at the terminal can be suitably used. The thiol-based material is, specifically, examples thereof include 4-cyano-1-butanethiol, 1, 11-undecanedithiol, 1, 16-hexadecanedithiol, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol, 2' - (ethylenedioxy) dithiol, 2, 3-butanedithiol, 5' -bis (mercaptomethyl) -2,2' -bipyridine, hexa (ethyleneglycol) dithiol, tetra (ethyleneglycol) dithiol, benzene-1, 4-dithiol, (11-mercaptoundecyl) hexa (ethyleneglycol) (11-mercaptoundecyl) tetrakis (ethylene glycol), 1-mercapto-2-propanol, 11-amino-1-undecanethiol, 11-amino-1-undecanethiolate, 11-azido-1-undecanethiol, 11-mercapto-1-undecanol, 11-mercaptoundecanamide, 11-mercaptoundecanoic acid, 11-mercaptoundecanohydroquinone, 11-mercaptoundecanophosphonic acid, 12-mercaptododecanoic acid, 16-amino-1-hexadecanethiol, 16-amino-1-hexadecanethiolate hydrochloride, 16-mercaptohexadecanoamide, 16-mercaptohexadecanoic acid, 3-amino-1-propanethiol, 3-amino-1-propanethiol hydrochloride, 3-mercapto-1-propanol, 3-mercaptopropionic acid, 4-mercapto-1-butanol, 6-amino-1-hexanethiol hydrochloride, 6-mercapto-1-hexanol, 6-mercaptohexanoic acid, 8-amino-1-octanethiol, 8-mercapto-1-octanol, 8-mercaptooctanoic acid, 9-mercapto-1-nonanol, 1, 4-benzenedimethanethiol, 4 '-bis (mercaptomethyl) biphenyl, 4' -dimercapto stilbene, 4-mercaptobenzoic acid, biphenyl-4, 4-dithiol, and the like.

Examples of the method for forming the layer made of the coating material include coating, vapor deposition, and sol-gel method. The thickness of the layer made of the coating material is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 1 μm or less, from the viewpoint of preventing warpage of the support. The thickness is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more, from the viewpoint of adhesion.

In the case where the support in the present embodiment has an adhesive layer, the phosphorus-containing organic material may have one or more kinds of adhesive structures. The bonding structure described in the item "(coating material)" is exemplified as the bonding structure. The binding structure is particularly preferably at least one structure selected from the group consisting of a hydroxyl group, an amino group, a phosphonic acid ester group, and an isocyanate group. When the layer having the conductive pattern region contains a phosphorus-containing organic material having such a bonding structure, the adhesion with the adhesion layer tends to be good.

< constitution of structure having conductive pattern region: embodiment 2 ]

Fig. 3 is a schematic cross-sectional view showing a structure having a conductive pattern region according to embodiment 2. As shown in fig. 3, the structure 20 having the conductive pattern region includes a support 21 and a layer 24 disposed on a surface formed by the support 21. In the layer 24, the insulating region 22 containing copper oxide and phosphorus and the conductive pattern region 23 containing reduced copper are disposed adjacent to each other. Furthermore, an oxygen barrier layer 25 is provided in the manner of a cover layer 24. The oxygen barrier layer 25 is light-permeable.

The insulating region 22 may be formed to contain copper oxide and hydrazine or hydrazine hydrate, or may be formed to contain copper oxide, phosphorus, and hydrazine or hydrazine hydrate. The conductive pattern region 23 may be formed to contain copper and phosphorus. The layer 24 in this embodiment may show the following constitution: a conductive pattern region 23 containing copper and an insulating region 22 containing copper oxide and phosphorus are adjacent to each other; or a structure in which the conductive pattern region 23 containing copper and the insulating region 22 containing copper oxide and hydrazine or hydrazine hydrate are adjacent to each other; or the conductive pattern region 23 containing copper and phosphorus and the insulating region 22 containing copper oxide and phosphorus are adjacent to each other. Alternatively, layer 24 may be formed as follows: a conductive pattern region 23 containing copper and an insulating region 22 containing copper oxide, hydrazine or hydrazine hydrate and phosphorus are adjacent to each other; or a constitution in which the conductive pattern region 23 containing copper and phosphorus and the insulating region 22 containing copper oxide, hydrazine or hydrazine hydrate and phosphorus are adjacent to each other.

The structure 20 in embodiment 2 is different from the structure 10 in embodiment 1 in that it has a resin layer (oxygen barrier layer 25).

With the configuration of embodiment 2, the conductive pattern regions containing copper can be insulated from each other by the insulating region containing copper oxide and a phosphorus-containing organic material, and thus, it is not necessary to remove the unfired portion of the layer 24 for production. Therefore, the number of manufacturing steps can be reduced, and the manufacturing cost can be reduced because a solvent or the like is not required. In addition, the insulating region is used to insulate the conductive pattern region, and the insulating region is less likely to crack, thereby improving reliability.

Further, since the layer 24 is covered with the resin layer (oxygen barrier layer 25), the conductive pattern region and the insulating region can be protected from external stress, and the long-term reliability of the structure having the conductive pattern region can be improved.

The respective configurations of the support 21, the insulating region 22, the conductive pattern region 23, and the layer 24 constituting the structure 20 are applicable to the respective configurations of the support 11, the insulating region 12, the conductive pattern region 13, and the layer 14 described above. The structure 20 may include the above-described adhesive layer.

The resin layer will be described in detail.

< resin layer >

As shown in fig. 3, the resin layer is disposed so as to cover the surface of the layer 24.

(oxygen Barrier layer)

An example of the resin layer is an oxygen barrier layer 25. In the method for producing the structure 20 described later, the oxygen barrier layer 25 can prevent the coating layer (described later) from coming into contact with oxygen during light irradiation, and can promote reduction of copper oxide. Thus, for example, an apparatus for realizing a vacuum atmosphere or an inert gas atmosphere, which causes the periphery of the coating layer to be an oxygen-free or low-oxygen atmosphere during light irradiation, is not required, and the manufacturing cost can be reduced.

The oxygen barrier layer 25 can prevent the conductive pattern region 23 from being peeled off or scattered due to heat generated by light irradiation. This enables the structure 20 to be manufactured with high yield.

(sealing Material layer)

Other examples of the resin layer are a sealing material layer. Fig. 4 is a schematic cross-sectional view showing another example of a structure having a conductive pattern region, which is different from that of fig. 3. The structure 30 having the conductive pattern region shown in fig. 4 has the same structure as the structure 20 shown in fig. 3 except that the sealing material layer 31 covers the surface of the cover layer 24 instead of the oxygen barrier layer 25 (see fig. 3).

The sealing material layer 31 is for example reconfigured after peeling off the oxygen barrier layer 25.

The oxygen barrier layer 25 (see fig. 3) plays an important role mainly in manufacturing. In contrast, the sealing material layer 31 can protect the conductive pattern region 23 from external stress in the finished product (the structure body 30 itself having the conductive pattern region and the product including the same) after manufacturing, and can improve the long-term stability of the structure body 30 having the conductive pattern region.

In this case, the sealing material layer 31 as an example of the resin layer preferably has a moisture permeability of 1.0g/m ² And/day or less. This is to ensure long-term stability, sufficiently reduce moisture permeability, prevent moisture from being mixed from the outside of the sealing material layer 31, and suppress oxidation of the conductive pattern region 23.

The sealing material layer 31 is an example of a functional layer that imparts a function to the structure 30 having the conductive pattern region after the oxygen barrier layer 25 is peeled off, and may be provided with scratch resistance when the structure 30 having the conductive pattern region is handled, stain resistance for preventing contamination from the outside, or rigidity by using a tough resin.

In the present specification, the functional layer such as the sealing material layer other than the oxygen barrier layer is simply referred to as "other resin layer".

The present embodiment will be described by taking the following cases as examples: in a method for manufacturing a structure having a conductive pattern region (described later), the oxygen barrier layer 25 is disposed so as to cover the coating layer (see fig. 3), the oxygen barrier layer 25 is removed after the photo-firing treatment, and the sealing material layer 31 (see fig. 4) as an example of the other resin layer is disposed so as to cover the coating layer 24. That is, the structure 20 (see fig. 3) can be said to be a precursor structure for obtaining the structure 30 (see fig. 4) having the conductive pattern region as a completed product. However, the structure 20 (see fig. 2) in which the oxygen barrier layer 25 remains as it is may be used as a finished product.

The resin constituting the resin layer preferably has a melting point of 150 ℃ to 300 ℃. The use of such a resin is preferable because it ensures a safety rate of 2 times or more the practical use temperature range (75 ℃ maximum), and enables lamination coating by hot melting when forming the resin layer.

The resin layer is preferably provided with an opening. The opening is provided so that the electrical contact portion can be mounted on the opening by a method such as metal plating or soldering in order to electrically connect the conductive pattern region from the outside.

The resin layer will be described in more detail. The oxygen barrier layer will be described first. The oxygen barrier layer prevents oxygen from being mixed into the coating layer from the outside during irradiation of light. For example, the following materials may be used as the material of the oxygen barrier layer. It is possible to use a polyester resin composed of polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate (PEN), polyester, polycarbonate (PC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacetal (POM), polyarylate (PAR), polyamide (PA), polyamideimide (PAI), polyetherimide (PEI), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyphthalamide (PPA), polyethernitrile (PENt), polybenzimidazole (PBI), polycarbodiimide, polysiloxane, polymethacrylamide nitrile rubber, acrylic rubber, polytetrafluoroethylene, epoxy resin, phenol resin, melamine resin, urea resin, polymethyl methacrylate resin (PMMA), and/or poly (methyl methacrylate) polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene (PMP), polystyrene (PS), styrene-butadiene copolymer, polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), novolac, benzocyclobutene, polyvinylphenol, polyethylene (PE), polyvinyl chloride (PVC), polyetheretherketone (PEEK), and the like, polychloroprene, polyoxymethylene, polysulfone (PSF), polyphenylsulfone resin (PPSU), cycloolefin polymer (COP), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (AS), nylon resin (PA 6, PA 66), polybutyl terephthalate resin (PBT), polyethersulfone resin (PESU), polytetrafluoroethylene resin (PTFE), polytrifluoroethylene (PCTFE), silicone resin, and the like.

In addition, an adhesive layer may be provided between the oxygen barrier layer and the coating layer to bond the oxygen barrier layer to the coating layer.

Next, the other resin layers will be described. The sealing material layer, which is an example of the other resin layer, can ensure long-term stability. The sealing material layer preferably has a sufficiently low moisture permeability. This is to prevent moisture from being mixed from the outside of the sealing material layer and to suppress oxidation of the conductive pattern region. The moisture permeability of the sealing material layer is preferably 1.0g/m ² Preferably less than/day, more preferably 0.5g/m ² Preferably not more than/day, more preferably 0.1g/m ² And/day or less. By using a sealing material layer having a moisture permeability in such a range, resistance change due to oxidation of the conductive pattern region can be suppressed in a long-term stability test under an environment of 85 ℃, for example.

The material that can be used for the sealing material layer may be selected from the same materials as the oxygen barrier layer described above, for example, fine particles composed of silicon oxide or aluminum oxide may be further mixed with these materials, or a layer composed of silicon oxide or aluminum oxide may be provided as a moisture barrier layer on the surface of these materials, thereby reducing moisture permeability.

The sealing material layer is not necessarily made of a single material, and a plurality of the above materials may be used.

The above-described structure having the conductive pattern region is manufactured using a laminate as an intermediate described below. That is, in order to obtain a desired structure having a conductive pattern region, it is necessary to optimize the structure of the laminate as an intermediate. Therefore, the structure of the laminate in the present embodiment will be described below.

< summary of the laminate of the present embodiment >

The inventors of the present invention arranged a coating layer containing copper oxide on the surface of a support, and selectively irradiated the coating layer with light to reduce the copper oxide to copper, thereby forming a conductive pattern region. In this case, it was found that if the electrical insulation of the region containing unreduced copper oxide is improved, the region can be left intact without being removed to ensure insulation between the conductive pattern regions, and the step of removing the region is not required.

It has further been found that by providing a resin layer on a coating layer, when firing treatment (hereinafter referred to as "photo-firing treatment") of copper oxide is performed by irradiation of light, equipment for realizing a vacuum atmosphere or an inert gas atmosphere is not required, and the manufacturing cost of the above-described structure having a conductive pattern region can be reduced, leading to completion of the present invention.

That is, as shown in fig. 5, the laminate 40 in the present embodiment is characterized by comprising a support 41, a coating layer 44 containing copper oxide and phosphorus disposed on a surface constituted by the support 41, and an oxygen barrier layer 45 as an example of a resin layer disposed so as to cover the coating layer 44. The oxygen barrier layer 45 is light-permeable.

As shown in fig. 5, an adhesive layer 46 is disposed between the coating layer 44 and the oxygen barrier layer 45 as needed.

As shown in fig. 5, since the coating layer 44 is covered with the resin layer (oxygen barrier layer 45), the coating layer 44 can be prevented from coming into contact with oxygen at the time of photo-firing, and the reduction of copper oxide can be promoted. Thus, no equipment for forming the surroundings of the coating layer 44 into an oxygen-free or low-oxygen atmosphere is required at the time of light irradiation, and the manufacturing cost can be reduced. Therefore, by using the laminate of the present embodiment, a desired laminate with a conductive pattern region can be manufactured with high accuracy and at low cost.

The respective configurations of the support 11 and the resin layer (oxygen barrier layer 25) described above are applied to the support 41 and the resin layer (oxygen barrier layer 45 as an example in fig. 5) constituting the laminate 40. The laminate 40 may include the above-described adhesive layer between the support 41 and the coating layer 44.

The coating layer 44 and the adhesive layer 46 are described in detail below.

< coating layer >

The coating layer 44 is formed by applying a dispersion, which is obtained by dispersing copper oxide in a dispersion medium using phosphorus that also functions as a dispersing agent, particularly a phosphorus-containing organic substance, to the surface constituted by the support 41.

Details of the preparation process of the phosphorus-containing organic matter, the dispersion medium and the dispersion are described below.

The coating layer 44 is formed with substantially the same composition as the insulating region 22 of fig. 3.

In addition, as in the insulating

regions

12 and 22 shown in fig. 1 and 3, the fine particles containing copper oxide are mixed with the phosphorus-containing organic material in the coating layer 44, and the content of the phosphorus-containing organic material is preferably 5 parts by volume or more and 900 parts by volume or less, based on 100 parts by volume of the total volume of the fine particles of copper oxide. Thus, the coating layer 44 having high flexibility, being less likely to crack even when bent, and being capable of forming a good conductive pattern region by firing can be obtained.

The coating layer 44 preferably further contains copper particles, and the mass ratio of copper particles/copper oxide fine particles in the coating layer is preferably 1.0 to 7.0. This can suppress the occurrence of cracks and can form a good conductive pattern region by firing.

The content of the copper oxide fine particles with respect to the coating layer 44 is preferably 10% by volume or more and 90% by volume or less. Thus, when the coating layer 44 is fired, the particles are easily fused to each other, and conductivity is exhibited. In addition, the coating layer 44 can be effectively attached to the support or the adhesive layer.

The average particle diameter (average primary particle diameter) of the copper oxide fine particles contained in the coating layer 44 is preferably 1nm to 50 nm. Thereby, the firing temperature for the coating layer 44 can be reduced, and the dispersibility of the copper oxide fine particles in the coating layer 44 can be improved.

The coating layer 44 may be formed to contain copper oxide and hydrazine or hydrazine hydrate, or may be formed to contain copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate. By including hydrazine or hydrazine hydrate, copper oxide is readily reduced to copper upon exposure to light.

< adhesive layer >

The adhesive layer 46 is disposed between the coating layer 44 and the oxygen barrier layer 45 as necessary, and the oxygen barrier layer 45 is bonded to the surface of the coating layer 44.

The adhesive force of the adhesive layer 46 is preferably 5mN/10mm or more and 10N/10mm or less. By setting the adhesive force to 5mN/10mm or more and less than 1N/10mm, the oxygen barrier layer 45 can be fixed to the coating layer 44 by the adhesive layer 46, and the oxygen barrier layer 45 can be easily peeled off in a later step. In addition, by setting the adhesive force to 1N/10mm or more and 10N/10mm or less, the oxygen barrier layer 45 can be firmly fixed to the coating layer 44 by the adhesive layer 46.

The adhesive layer 46 is an adhesive sheet, an adhesive film, or an adhesive material. The pressure-sensitive adhesive included in the pressure-sensitive adhesive layer 46 is not particularly limited, and examples thereof include an acrylate resin, an epoxy resin, and a silicone resin.

In the case where the oxygen barrier layer 45 is a resin film having the adhesive layer 46, the oxygen barrier layer 45 can be easily formed by bonding the resin film to the surface of the coating layer 44, which is preferable. In addition, by selecting the adhesive force as described above, the oxygen barrier layer 45 can be peeled off as needed. By peeling the oxygen barrier layer 45 in this manner, the structure 10 having the structure shown in fig. 2 can be obtained.

In the case where the oxygen barrier layer 45 is a layer formed of a cured resin or a layer formed by heating and extrusion-laminating a thermoplastic resin, the adhesive layer may be omitted.

In the present embodiment, a layer containing silicon oxide or aluminum oxide is preferably provided between the coating layer 44 and the resin layer. The layer containing silicon oxide or aluminum oxide can function as a moisture barrier layer, and can reduce moisture permeability.

Fig. 6 is a cross-sectional view of a structure 50 having a conductive pattern region formed using the laminate shown in fig. 5. As shown in fig. 6, the structure 50 having the conductive pattern region includes: a support body 51; a layer 54 in which an insulating region 52 containing copper oxide and a phosphorus-containing organic material and a conductive pattern region 53 containing reduced copper are disposed adjacent to each other on a surface constituted by the support 51; an oxygen barrier layer 55 as an example of a resin layer provided as the cover layer 54; and an adhesive layer 56 interposed between the layer 54 and the oxygen barrier layer 55.

The structure 50 having the conductive pattern region shown in fig. 6 has basically the same structure as the structure 20 shown in fig. 3, but in fig. 6, an adhesive layer 56 is interposed between a layer 54 and an oxygen barrier layer 55, which is different from fig. 3. In fig. 6, by providing the adhesive layer 56, adhesion between the oxygen barrier layer 55 and the layer 54 can be improved, and the structure 50 having the conductive pattern region with excellent durability can be realized. Further, the moisture barrier property can be improved by sandwiching a layer containing silicon oxide or aluminum oxide between the oxygen barrier layer 55 and the layer 54.

In fig. 6, the oxygen barrier layer 55 may be replaced with another resin layer as needed. At this time, by using an adhesive having weak adhesion in advance in the adhesive layer 56, the oxygen barrier layer 55 can be easily peeled from the layer 54. The adhesive layer 56 may be interposed between the other resin layer and the layer 54, or a layer containing silicon oxide or aluminum oxide may be interposed therebetween. When the other layer is directly bonded to the surface of the layer 54 without sandwiching the adhesive layer 56 or the layer containing silicon oxide or aluminum oxide, the structure 50 having the conductive pattern region according to the structure shown in fig. 3 is obtained.

< summary of copper wiring of the present embodiment >

In the above-described structure, the present inventors developed a copper wiring including a conductive pattern region. That is, in this embodiment, the conductive pattern region of the layer adjacent to the insulating region is a copper wiring described below. In this embodiment, the insulating region may be removed to obtain a copper wiring.

The copper wiring in the present embodiment includes reduced copper in which copper oxide is reduced, phosphorus, and carbon. And is characterized in that the elemental concentration ratio of phosphorus/copper is 0.02 to 0.30, and the elemental concentration ratio of carbon/copper is 1.0 to 6.0. The arithmetic average roughness Ra of the surface of the copper wiring is preferably 20nm to 500 nm.

As described above, the content of the phosphorus element is preferably in the range of 0.02 to 0.30 inclusive with respect to the element of copper. More preferably, the range is from 0.05 to 0.28, and still more preferably, the range is from 0.1 to 0.25. The concentration of phosphorus/copper element is preferably 0.02 or more, whereby oxidation of copper can be suppressed, and reliability as a copper wiring circuit can be improved. Further, it is preferable that the element concentration of phosphorus/copper is 0.30 or less, so that the resistance value of the wiring can be reduced.

As described above, the content of the carbon element is preferably in the range of 1.0 to 6.0 with respect to the copper element. More preferably 1.5 to 5.5, and still more preferably 2.0 to 5.0. By setting the elemental concentration of carbon/copper to 1.0 or more, the flexibility of the copper wiring can be borne. Further, it is preferable that the element concentration of carbon/copper is 6.0 or less, so that the resistance value of the wiring can be reduced.

Carbon is derived from residues generated when copper oxide is reduced by organic components such as phosphorus-containing organic matters and glycols in the coating layer.

As described above, ra is preferably 20nm to 500 nm. Ra is more preferably 50nm to 300nm, still more preferably 50nm to 200 nm. Ra is the arithmetic average roughness of the surface of the copper wiring, and when the copper wiring is covered with the resin layer, ra is the surface roughness of the surface in contact with the resin layer. It is preferable that Ra is 20nm to 500nm, because adhesion to the resin layer can be improved.

The copper wiring may further contain nitrogen. The element concentration ratio of nitrogen/copper is preferably 0.04 to 0.6, more preferably 0.1 to 0.55, and still more preferably 0.2 to 0.5. The corrosion resistance of the copper wiring can be improved by setting the elemental nitrogen/copper concentration ratio to 0.04 or more, and the resistance value of the wiring can be reduced by setting the elemental nitrogen/copper concentration ratio to 0.6 or less, which is preferable. Nitrogen originates from residues generated when hydrazine or hydrazine hydrate in the coating layer reduces copper oxide.

The copper wiring preferably contains reduced copper in which copper oxide is reduced, phosphorus, and carbon, and the concentration ratio of each element, that is, phosphorus: carbon: copper is preferably 0.02:1:1 to 0.3:6: 1. More preferably, the concentration ratio is 0.05:1.5:1 to 0.28:5.5:1, more preferably 0.1:2:1 to 0.25:5: 1. The above range is a ratio defined by setting the elemental concentration of copper to 1. By containing reduced copper, phosphorus, and carbon in this range, the resistance value of the wiring can be reduced, and the copper oxidation inhibition and copper bendability can be collectively supported to the maximum extent.

The copper wiring preferably contains reduced copper, phosphorus, carbon, and nitrogen in which copper oxide is reduced, and the concentration ratio of each element, that is, phosphorus: carbon: nitrogen: copper is preferably 0.02:1:0.04:1 to 0.3:6:0.6: 1. More preferably, the concentration ratio is 0.05:1.5:0.1:1 to 0.28:5.5:0.55:1, more preferably 0.1:2:0.2:1 to 0.25:5:0.5: 1. The above range is a ratio defined by setting the elemental concentration of copper to 1. By containing reduced copper, phosphorus, carbon, and nitrogen in this range, the resistance value of the wiring can be reduced, and copper oxidation inhibition, copper bendability, and corrosion resistance can be collectively supported to the maximum extent.

Next, a method for manufacturing the 1 st structure 10 shown in fig. 2 will be described. The method for manufacturing the 1 st structure 10 mainly includes the following steps.

(A) A step of disposing a coating layer containing copper oxide and a phosphorus-containing organic substance on a surface constituted by a support,

(B) And a step of reducing copper oxide to copper by selectively irradiating the coating layer with light, thereby obtaining a support, and a layer in which an insulating region including copper oxide and the phosphorus-containing organic material and a conductive pattern region including copper are disposed adjacent to each other on a surface constituted by the support.

In the above (a), a coating layer containing copper oxide and hydrazine or hydrazine hydrate may be disposed on the surface constituted by the support. Alternatively, a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate may be disposed on the surface constituted by the support. By including hydrazine or hydrazine hydrate, reduction by light can be further performed, and a copper film having low resistance can be obtained.

As shown in (a) above, a coating layer containing copper oxide and phosphorus is first disposed on the surface constituted by the support. The method may be: (a) A method of coating a dispersion containing copper oxide and a phosphorus-containing organic compound; (b) A method of dispersing copper oxide fine particles and then coating a phosphorus-containing organic material; (c) A method of coating a phosphor-containing organic material and then dispersing copper oxide particles; etc. The method (a) is described below as an example, but is not limited thereto.

(method for producing Dispersion)

The method for producing the dispersion will be described. Copper oxide particles and phosphorus-containing organic matter are dispersed in a dispersion medium to prepare copper oxide dispersion.

For example, the copper oxide fine particles synthesized by the method of (3) above are soft aggregates and are not suitable for direct coating, and therefore need to be dispersed in a dispersion medium.

After the synthesis in the method (3) is terminated, the synthesis solution and the copper oxide fine particles are separated by a known method such as centrifugation. The obtained copper oxide fine particles are added with a dispersion medium and a phosphorus-containing organic material, and stirred by a known method such as a homogenizer to disperse the copper oxide fine particles in the dispersion medium.

The phosphorus-containing organic material according to the present embodiment functions as a dispersant. However, other dispersant may be added in a range that does not affect the electrical insulation of the insulating region (insulating region 12 shown in fig. 2).

The copper oxide fine particles are not easily dispersed by the dispersion medium, and the dispersion may be insufficient. In such a case, copper oxide is dispersed using, for example, an easily dispersible alcohol (for example, butanol or the like), and then replaced with a desired dispersion medium and concentrated to a desired concentration. As an example, there is a method of concentrating by a UF membrane and repeatedly diluting and concentrating by repeatedly using a desired dispersion medium.

(coating)

A film composed of the dispersion according to the present embodiment is formed on the surface of the support. More specifically, for example, the dispersion is coated on a support, and the dispersion medium is removed by drying as needed to form a coating layer. The method for forming the coating layer is not particularly limited, and coating methods such as die coating, spin coating, slot coating, bar coating, doctor blade coating, spray coating, and dip coating can be used. The dispersions are preferably applied to the support in uniform thickness using these methods.

The oxygen barrier layer is preferably disposed so as to cover the coating layer disposed on the support. Here, as a method for manufacturing the structure 10 shown in fig. 2, the arrangement of the oxygen barrier layer is not necessarily required.

(firing treatment)

As described in (B), in the present embodiment, the conductive pattern region is formed by performing the heat treatment under the condition that copper oxide in the coating layer is reduced to form copper particles and the formed copper particles are welded to each other to form an integrated structure.

In this embodiment, a selective light irradiation method is used as a method of firing treatment. In the present embodiment, as the photo-firing method, for example, a flash method or a laser method using a discharge tube such as xenon as a light source can be applied. These methods can fire a coating layer formed on a support by exposing light having a high intensity to light in a short time and raising the temperature to a high temperature in a short time. Since the firing time is short, the damage to the support is small, and the resin film substrate having low heat resistance can be applied.

The flash method is a method of instantaneously discharging charges stored in a capacitor using, for example, a xenon lamp (discharge tube). According to this aspect, a large amount of pulsed light (xenon lamp light) can be generated, and the coating layer formed on the support is irradiated, thereby instantaneously heating the coating layer to a high temperature. The exposure amount can be adjusted by the light intensity, the light emission time, the light irradiation interval and the number of times.

In order to form the conductive pattern region, light irradiation may be selectively performed on the coating layer by a light source through a mask.

The same effect can be obtained even when a laser source is used, although the light-emitting source is different. In the case of the laser source, there is a degree of freedom in wavelength selection in addition to the adjustment items of the flash system, and the selection may be made in consideration of the light absorption wavelength of the coating layer or the absorption wavelength of the support.

In addition, according to the laser system, exposure can be performed by scanning with a light beam, so that the exposure range can be easily adjusted, and the coating layer can be selectively irradiated with light (drawn) without using a mask.

As the type of the laser source, YAG (yttrium-aluminum-garnet), YVO (yttrium vanadate), yb (ytterbium), semiconductor laser (GaAs, gaAlAs, gaInAs), carbon dioxide, and the like can be used. As the laser light, not only fundamental waves but also harmonics may be picked up as needed.

In this embodiment, the light is preferably laser light having a center wavelength of 355nm to 532 nm. Since this wavelength is absorbed by the cuprous oxide-containing coating layer, the reduction of cuprous oxide is uniformly generated, and a region (conductive pattern region) having low electric resistance can be obtained.

In this embodiment, since the support is made light-permeable and light can pass through the support, a part of the coating layer can be properly fired.

In addition, if the oxygen barrier layer is provided on the surface of the coating layer, the support or the coating layer may be made light-permeable, and the support or the coating layer may be made light-permeable, or the coating layer may be made light-permeable through the support or the oxygen barrier layer may be made light-permeable through the coating layer, so that a part of the coating layer may be properly fired.

In addition, in the structure in which the oxygen barrier layer is disposed on the surface of the coating layer, the structure 10 shown in fig. 2 can be obtained by removing the oxygen barrier layer after forming the conductive pattern region.

A method for manufacturing a support having a conductive pattern region according to embodiment 1 will be described in more detail with reference to fig. 7. Fig. 7 is an explanatory diagram showing steps of the method for manufacturing the support with the conductive pattern region according to embodiment 1. In fig. 7 (a), copper acetate is dissolved in a mixed solvent of water and Propylene Glycol (PG), and hydrazine or hydrazine hydrate is added thereto and stirred.

Next, in fig. 7 (b) and (c), the supernatant and the precipitate are separated by centrifugation. Next, in fig. 7 (d), a dispersant and an alcohol are added to the obtained precipitate to disperse.

Next, in fig. 7 (e) and (f), concentration and dilution are repeated by the UF membrane module, and the solvent is replaced, thereby obtaining a dispersion I containing copper oxide fine particles.

In fig. 7 (g) and (h), dispersion I was applied to a PET support (referred to as "PET" in fig. 7 (h)) by a spray method to form a coating layer containing copper oxide and a phosphorus-containing organic substance (referred to as "Cu" in fig. 7 (h)) ₂ O”)。

Next, in fig. 7 (i), the coating layer is irradiated with laser light, and a part of the coating layer is selectively fired to reduce copper oxide to copper (referred to as "Cu" in fig. 7 (i)). As a result, in fig. 7 (j), a structure having a conductive pattern region in which a layer including an insulating region (denoted by "a" in fig. 7 (j)) including copper oxide and phosphorus and a conductive pattern region (denoted by "B" in fig. 7 (j)) including copper are formed adjacent to each other on a support is obtained.

In this embodiment, the insulating region may be further removed by cleaning. A method in which copper wiring (indicated by "C" in fig. 7 (k)) is patterned on a support can be obtained. The copper wiring C is the same layer as the conductive pattern region B. The copper wiring C and the support between the copper wirings C may be sealed with a second resin layer (denoted by "D" in fig. 7 (l)). The second resin layer D may be formed so as to cover at least the copper wiring C as the conductive pattern region B. The second resin layer corresponds to the "other resin layer" mentioned above.

In the case of removing the insulating region, water, alcohols such as ethanol, propanol, butanol, isopropanol, methanol, ethylene glycol, and glycerin, and organic solvents such as ketones, esters, and ethers may be used. Particularly preferred are water, ethanol, propanol, butanol and isopropanol from the viewpoint of cleaning performance of the insulating region. In addition, a phosphorus-based dispersant may be added to the solvent. The cleaning performance can be further improved by adding a phosphorus-based dispersant.

In manufacturing the structure 10 shown in fig. 2, the structure 10 can be manufactured without using the laminate 40 shown in fig. 5, for example, in a vacuum atmosphere or the like, even if an oxygen barrier layer (fig. 7 (h)) as an example of a resin layer is not present. However, it is needless to say that the use of a laminate including an oxygen barrier layer eliminates the need for equipment for realizing a vacuum atmosphere or an inert gas atmosphere, and thus has an advantage of reducing the manufacturing cost of a structure having a conductive pattern region.

Next, in the method for manufacturing the 2

nd structures

20, 30, 50 shown in fig. 3, 4, and 6 described above, the laminate 40 shown in fig. 5 is preferably used.

That is, the 2 nd manufacturing method of the structure having the conductive pattern region includes the following steps.

(C) A step of disposing a coating layer containing copper oxide and a phosphorus-containing organic substance on a surface constituted by a support,

(D) A step of disposing a resin layer (first resin layer) so as to cover the coating layer,

(E) And a step of reducing copper oxide to copper by selectively irradiating light to the coating layer through either the resin layer or the support, thereby obtaining a structure having the support, a layer in which an insulating region including copper oxide and a phosphorus-containing organic substance and a conductive pattern region including copper are disposed adjacent to each other on a surface constituted by the support, and a resin layer formed so as to cover the layer.

In the above (C), the coating layer containing copper oxide and hydrazine or hydrazine hydrate may be disposed on the surface constituted by the support. Alternatively, a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate may be disposed on a surface of the support. By including hydrazine or hydrazine hydrate, reduction by light can be further performed, and a copper film having low resistance can be obtained.

The step (C) is the same as the step (A) described above. (D) In the step (a), a resin layer is formed on the surface of the coating layer. By the steps of obtaining (C) and (D), a laminate 40 as an intermediate shown in fig. 5 can be produced.

That is, the method for manufacturing the laminate 40 includes the steps of: a step of disposing a coating layer containing copper oxide and a phosphorus-containing organic material on a surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) so as to cover the coating layer. Alternatively, the method for producing the laminate 40 includes the steps of: a step of disposing a coating layer containing copper oxide, hydrazine or hydrazine hydrate on a surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) so as to cover the coating layer. Alternatively, the method for producing the laminate 40 includes the steps of: a step of disposing a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate on a surface formed by a support; and a step of disposing a resin layer (oxygen barrier layer 45) so as to cover the coating layer.

In the laminate 40 shown in fig. 5, the oxygen barrier layer 45 is adhered to the coating layer 44 via the adhesive layer 46. Wherein the adhesive layer 46 is not necessary. For example, in the case where the oxygen barrier layer 45 is formed of a resin cured product or in the case where the thermoplastic resin is heated and extrusion-laminated, the adhesive layer 46 is not necessarily required. For example, the material constituting the oxygen barrier layer may be softened by heating and pressed against the coating layer while applying pressure, and the laminate may be formed by lamination.

The oxygen barrier layer 45 is exemplified as an example of the resin layer, and the resin layer is preferably an oxygen barrier layer and a resin film having an adhesive layer. Thus, the laminate 40 shown in fig. 5 can be simply and properly produced by adhering the resin film to the surface of the coating layer 44.

The binder is not particularly limited, and examples thereof include acrylate resins, epoxy resins, silicone resins, and the like.

The adhesive force of the adhesive layer is preferably 5mN/10mm or more and 10N/10mm or less. This makes it possible to appropriately fix the oxygen barrier layer to the coating layer via the adhesive layer, and to easily peel the oxygen barrier layer in a later step. In addition, by setting the adhesive force to 1N/10mm or more and 10N/10mm or less, the oxygen barrier layer can be firmly fixed to the coating layer by the adhesive layer.

The laminate formed by the steps (C) and (D) is subjected to the firing treatment to form a conductive pattern region.

In this embodiment, either the oxygen barrier layer or the support is made light-permeable. Thus, when the light irradiation method is performed, light can be transmitted through the oxygen barrier layer or the support to fire a part of the coating layer.

As described above, the structure 20 shown in fig. 3 and the structure 50 having the conductive pattern region shown in fig. 6 can be manufactured.

(arrangement of other resin layers)

Next, the oxygen barrier layer may be replaced with another resin layer as needed. The oxygen barrier layer is first removed by dissolution with a solvent. In this case, when the adhesive layer is formed using the above adhesive layer, only the adhesive layer may be dissolved and removed by a solvent. In addition, the oxygen barrier layer is peeled from the layer having the conductive pattern region by using an adhesive having weak adhesion in advance, whereby the oxygen barrier layer can be peeled without using a solvent.

Then, a sealing material layer as an example of the other resin layer is disposed so as to cover the exposed layer having the conductive pattern region. The sealing material layer may be formed by bonding a resin sheet formed of the material constituting the sealing material layer to the coating layer with an adhesive prepared separately.

The sealing material layer may be formed by heating the material constituting the sealing material layer to soften the material, and pressing the material against the coating layer while applying pressure to perform lamination processing. Further, a curable material that is cured by light or heat may be selected, and a coating layer made of a curable material may be formed on the exposed layer having the conductive pattern region, and then cured by light or heat.

A method for manufacturing a support with a conductive pattern region according to embodiment 2 will be described more specifically with reference to fig. 8. Fig. 8 is an explanatory diagram showing steps of the method for manufacturing the support with the conductive pattern region according to the present embodiment. In fig. 8 (a), copper acetate is dissolved in a mixed solvent of water and Propylene Glycol (PG), and hydrazine or hydrazine hydrate is added thereto and stirred.

Next, in fig. 8 (b) and (c), the supernatant and the precipitate are separated by centrifugation. Next, in fig. 8 (d), a dispersant and an alcohol are added to the obtained precipitate to disperse.

Next, in fig. 8 (e) and (f), concentration and dilution by the UF membrane module are repeated to replace the solvent, thereby obtaining a dispersion I containing copper oxide fine particles.

In fig. 8 (g) and (h), dispersion I was applied to a PET support (referred to as "PET" in fig. 8 (h)) by a spray method to form a coating layer containing copper oxide and a phosphorus-containing organic substance (referred to as "Cu" in fig. 8 (h)) ₂ O”)。

Next, in fig. 8 (i), an oxygen barrier layer is disposed on the coating layer (referred to as "barrier" in fig. 8 (i)).

Next, in fig. 8 (j), the coating layer is irradiated with laser light through the oxygen barrier layer, and a part of the coating layer is selectively fired to reduce copper oxide to copper (referred to as "Cu" in fig. 8 (j)). As a result, in fig. 8 (k), a layer is obtained in which an insulating region (denoted by "a" in fig. 8 (k)) containing copper oxide and a phosphorus-containing organic material and a conductive pattern region (denoted by "B" in fig. 8 (k)) containing copper are disposed adjacent to each other on the support.

Next, in fig. 8 (l) and (m), the oxygen barrier layer is removed by a solvent, and the layer adjacent to the conductive pattern region and the insulating region is exposed. Then, in fig. 8 (n), the surface of the layer adjacent to the insulating region in the conductive pattern region is covered with a sealing material layer (referred to as "sealing" in fig. 8 (n)), whereby the structure having the conductive pattern region shown in fig. 4 can be obtained.

In this embodiment, the insulating region may be further removed by cleaning. A method of patterning copper wiring (indicated by "C" in fig. 8 (o)) on a support can be obtained. The copper wiring C is the same layer as the conductive pattern region B. The copper wiring C and the support between the copper wirings C may be sealed with a second resin layer (denoted by "D" in fig. 8 (p)). The second resin layer D may be formed so as to cover at least the copper wiring C as the conductive pattern region B. The second resin layer corresponds to the "other resin layer" mentioned above.

The oxygen barrier layer may not be removed and may function as a sealing material layer. At this time, the structure having the conductive pattern region shown in fig. 3 and 6 can be manufactured. Therefore, in the method for manufacturing a structure having a conductive pattern region according to the present embodiment, a step after removal of the oxygen barrier layer is not necessary.

In the method for manufacturing the structure of the present embodiment, after the layer having the conductive pattern region and the insulating region is obtained by irradiation with light, as shown in fig. 7 (k) and 8 (o), the insulating region may be removed from the layer in close contact with the conductive pattern region and the insulating region. For example, the insulating region may be selectively cleaned and removed using an etching solution or the like that does not dissolve the conductive pattern region but dissolves the insulating region. In this embodiment, the boundary between the conductive pattern region and the insulating region can be clearly distinguished, and only the insulating region can be selectively removed as appropriate.

In the present embodiment, as described above, after the insulating region is removed from the layer, as shown in fig. 7 (l) and 8 (p), the second resin layer may be disposed so as to cover the surface of the conductive pattern region. This ensures insulation between the conductive pattern regions and each other. In addition, it is also effective as a barrier film in terms of durability of copper wiring. The second resin layer may be a "other resin layer" as mentioned above.

In this embodiment, for example, the insulating region may be removed as described above, and the copper wiring may be left on the support. The conductive pattern region containing reduced copper, phosphorus, and carbon, which is obtained by reducing copper oxide, remaining on the support can be manufactured as the copper wiring of the present embodiment. Alternatively, even if the insulating region is not removed, the conductive pattern region and the conductive pattern region in the insulating region can be regarded as copper wiring. In this case, in the copper wiring in this embodiment, the elemental concentration ratio of phosphorus to copper may be set to 0.02 to 0.30, the elemental concentration ratio of carbon to copper may be set to 1.0 to 6.0, and Ra may be set to 20nm to 500 nm. In order to set the elemental concentration ratio of phosphorus to copper to 0.02 to 0.30, for example, a coating layer containing copper oxide and a phosphorus-containing organic material may be provided, and light irradiation may be performed to obtain reduced copper from the copper oxide. The element concentration ratio of phosphorus/copper can be adjusted by adjusting the ratio of copper oxide to phosphorus-containing organic matter. In order to set the carbon/copper ratio to 1.0 or more and 6.0 or less, a coating layer containing copper oxide and an organic substance may be provided, and light irradiation may be performed to obtain reduced copper from the copper oxide, for example, to manufacture the copper alloy. The element concentration ratio of carbon/copper can be adjusted by adjusting the ratio of copper oxide to organic matter. Further, in order to set the Ra of the surface of the copper wiring to 20nm to 500nm, for example, the desired Ra can be obtained by adjusting the light irradiation intensity, irradiation speed, and irradiation interval when light irradiation is performed.

In the method for producing a structure or a laminate having a conductive pattern region according to the present embodiment, the resin layer or the support preferably has a light transmittance at a wavelength of 445nm of 30% or more, more preferably 40% or more, and still more preferably 50% or more. The upper limit of the light transmittance may be 98% or less. Regarding the wavelength, wavelengths from near ultraviolet to near infrared such as 355nm, 405nm, 450nm, 532nm, 1064nm, etc. may be selected in addition to 445 nm. By increasing the light transmittance at such a wavelength, the coated layer can be fired by irradiation with light from the support side, thereby forming the conductive pattern region.

In the method for manufacturing a structure or a laminate having a conductive pattern region according to the present embodiment, copper oxide contained in the coating layer is preferably cuprous oxide. Thus, reduced copper can be obtained by firing, and a layer in which a conductive pattern region and an insulating region are mixed can be formed with high accuracy.

In the method for producing a structure or a laminate having a conductive pattern region according to the present embodiment, the phosphorus-containing organic material contained in the coating layer preferably has a skeleton represented by the following chemical formula (1) (in chemical formula (1), R is an ester salt).

[ chemical 5]

Chemical formula (1)

In the chemical formula (1), R is an ester salt.

The structure of the above chemical formula (1) can adsorb copper oxide and also has excellent adhesion to a support. This ensures insulation and effectively prevents peeling between the support and the coating layer.

In the method for manufacturing a structure or a laminate having a conductive pattern region according to the present embodiment, a case where the support is a three-dimensional object is exemplified. That is, in the present embodiment, the surface of the case, chassis, or the like may be used as the support surface, and the structure having the conductive pattern region in the present embodiment may be formed, for example, instead of the flat support.

< application example >

The structure having the conductive pattern region according to the present embodiment is suitably applicable to, for example, wiring materials such as electronic circuit boards (printed circuit boards, RFIDs, replacement of wire harnesses in automobiles, and the like), antennas formed in housings of portable information devices (smart phones and the like), mesh electrodes (electrode films for capacitive touch panels), electromagnetic wave shields, and heat dissipation materials.

As described above, according to the structure having the conductive pattern regions according to the present embodiment, the conductive pattern regions including copper can be insulated from each other by the insulating region including copper oxide and phosphorus. Therefore, it is not necessary to remove the unfired portion of the layer disposed on the support for production, and thus the production process can be reduced, and the production cost can be reduced because a solvent or the like is not required. In addition, the insulating region is used to insulate the conductive pattern region, and the insulating region is less likely to crack, thereby improving reliability.

In addition, according to the method for manufacturing a structure having a conductive pattern region according to the present embodiment, a portion of a coating layer including copper oxide and a phosphorus-containing organic material can be fired by laser to form a conductive pattern region, and an unfired portion can be used for insulation of the conductive pattern region. It is not necessary to remove the unfired portion of the coating layer. Therefore, the number of manufacturing steps can be reduced, and the manufacturing cost can be reduced because a solvent or the like is not required. In addition, since it is not necessary to provide a solder resist or the like for insulation of the conductive pattern region, the manufacturing process can be reduced accordingly.

In addition, according to the laminate of the present embodiment, the coating layer is covered with the resin layer, so that the coating layer can be prevented from coming into contact with oxygen during photo-firing, and reduction of copper oxide can be promoted. Thus, the device for forming the surroundings of the coating layer into an oxygen-free or low-oxygen atmosphere during light irradiation is not required, and the manufacturing cost can be reduced. In addition, since the coating layer is covered with the resin layer, the coating layer can be protected from external stress, and the handleability can be improved.

In addition, according to the method for manufacturing a laminate according to the present embodiment, a step of forming a coating layer containing copper oxide and a phosphorus-containing organic substance on a surface of a support and a step of forming a resin layer on a surface of the coating layer are used, whereby a laminate can be manufactured simply and appropriately.

Examples

The present invention will be described in more detail with reference to the following examples.

< production of Dispersion >

80g of copper (II) acetate monohydrate (manufactured by Wako pure chemical industries, ltd.) was dissolved in a mixed solvent composed of 800g of water and 400g of 1, 2-propanediol (manufactured by Wako pure chemical industries, ltd.) and 20g of hydrazine or hydrazine hydrate (manufactured by Wako pure chemical industries, ltd.) was added thereto and stirred, followed by separation into a supernatant and a precipitate by centrifugation.

To 2.8g of the obtained precipitate were added 0.05g of DISPRBYK-145 (trade name, manufactured by Pick chemical Co., ltd.) (BYK-145 in Table 1) as a phosphorus-containing organic substance and 6.6g of ethanol (manufactured by Wako pure chemical industries, ltd.) as a dispersion medium, and the mixture was dispersed using a homogenizer. Further, dilution and concentration were repeatedly performed with ethanol, whereby a dispersion (a) containing cuprous oxide fine particles containing cuprous oxide (cupric oxide (I)) was obtained. The weight of the cuprous oxide particles in the precipitate was measured by vacuum drying the precipitate, and as a result, 2.0g of the cuprous oxide particles were contained in 2.8g of the precipitate.

The cuprous oxide particles obtained by vacuum drying were observed by a transmission electron microscope and analyzed by an energy-dispersive X-ray spectrometry, and as a result, the content (vol%) of cuprous oxide in the cuprous oxide particles was 100 vol% (see table 1).

The same operations as described above were carried out except that the amounts of the phosphorus-containing organic matters added to 2.8g of the precipitate were changed as described in table 1, respectively, to obtain dispersions (b) to (g) containing fine particles of cuprous oxide. The content (vol%) of copper oxide in all the fine particles contained in the dispersions (b) to (g) was measured and found to be 100 vol% (see table 1).

TABLE 1

Copper powder (average particle diameter 1 μm, spherical particles) was added to the dispersion (c) in the amounts shown in table 1 to obtain dispersions (h) and (i). The content (vol%) of copper oxide in all the particles (copper oxide particles and copper powder) contained in the dispersions (h), (i) was measured and found to be 59.7 vol% and 42.6 vol%, respectively (see table 1).

< preparation of sample >

[ samples 1 to 19]

After the surface of the support was subjected to UV ozone treatment, the dispersion was bar-coated to a predetermined thickness and dried at room temperature for 10 minutes, whereby a sample having a coating layer formed on the support was obtained.

Samples 1 to 19 were obtained by changing the types of the support, the dispersion and the thickness of the coating layer as shown in Table 2.

As the support PET, a PET film (cosmosine a4100 manufactured by eastern spinning corporation) having a thickness of 100 μm was used.

[ sample 20]

As a support, the surface of a PET film (Cosmoshine a4100 manufactured by eastern spinning corporation) having a thickness of 100 μm was subjected to UV ozone treatment, and then the surface was roughened by Reactive Ion Etching (RIE) treatment with oxygen gas to form an adhesive layer.

Next, the dispersion (c) was bar-coated on the sealing layer so as to have a predetermined thickness of 0.5. Mu.m, and dried at room temperature for 10 minutes, thereby obtaining a sample 20.

[ samples 21 to 23]

Samples 21 to 23 were obtained by the same operations as in the case of the sample 20 described above, except that the types of the supports were changed as described in table 2. The specific surface area and surface roughness of the obtained sealing layer were measured and are shown in table 2.

As the support, the following PEN film, PI film, and mpe sheet were used.

PEN film (manufactured by Teijin Film Solutions company, teonex Q65H, thickness 100 μm)

PI film (manufactured by Toli-DuPont company, KAPTON500H, 125 μm thick)

m-PPE sheet (manufactured by Asahi chemical Co., ltd., E1000, thickness 125 μm)

[ sample 24]

As a support, a coating liquid containing fine particles of silicon oxide (average particle diameter 25 nm) was applied to the surface of a PET film (Cosmoshine a4100 manufactured by eastern spinning corporation) having a thickness of 100 μm after UV ozone treatment. Then, the resultant was dried at room temperature for 30 minutes to form an adhesive layer having a thickness of 5. Mu.m.

Thereafter, the dispersion (a) was changed to the dispersion (c), and the sample 24 was obtained by the same operation as in the case of the above-mentioned samples 1 to 19.

[ sample 25]

As a support, a surface of a PET film (manufactured by eastern spinning corporation, cosmoshine a 4100) having a thickness of 100 μm was subjected to UV ozone treatment, and then a coating liquid containing alumina fine particles (average particle diameter 110 nm) was applied by a blade coater. Then, the resultant was dried at room temperature for 30 minutes to form an adhesive layer having a thickness of 10. Mu.m.

Thereafter, the dispersion (a) was changed to the dispersion (c), and the sample 25 was obtained by the same operation as in the case of the above-mentioned samples 1 to 19.

< evaluation and measurement method >

(evaluation of film Forming Property of Dispersion)

The film forming properties of the coating layer of the obtained sample were observed by a shape measuring laser microscope (manufactured by KEYENCE Co., ltd., VK-9510). At this time, a 10-fold objective lens was used. The evaluation criteria are as follows. Fig. 9 and 10 are electron micrographs for explaining a crack state in the coating layer of the example. Fig. 9 shows an example of a cracked coating layer, and fig. 10 shows an example of a cracked coating layer.

(firing with laser and evaluation of conductivity)

The substrate of the sample in an argon atmosphere was irradiated with laser light (wavelength 445nm, output 1.2W, continuous Wave (CW)) while moving the focal position at a maximum speed of 300 mm/min by using an electric scanner, whereby a desired conductive pattern region containing copper was obtained in a size of 25mm×1 mm.

The method of evaluating the conductivity is as follows. The conductivity was evaluated by contacting both ends of the conductive pattern area with a tester. The evaluation criteria are as follows.

O: resistance value is less than 1kΩ

Delta: resistance value is 1kΩ or more and less than 1mΩ

X: resistance value is 1MΩ or more

(firing with xenon flash and conductivity evaluation)

A30 mm square sample was placed on a sample stage in an argon atmosphere. A light-shielding mask having an opening with a size of 25mm×1mm was placed thereon, and a xenon flash (irradiation energy 3J/cm) was further irradiated from the light-shielding mask ² Irradiation time 4 ms). Thus, a conductive pattern region containing copper was obtained in a size of 25mm×1 mm. The portion of the light shielding mask which is not the opening is in the same state as before the xenon flash is irradiated.

The conductivity was evaluated by contacting both ends of the conductive pattern area with a tester. The evaluation criteria are as follows.

O: resistance value is less than 1kΩ

Delta: resistance value is 1kΩ or more and less than 1mΩ

X: resistance value is 1MΩ or more

In firing by laser light and firing by xenon flash, any material can be used as a support having a conductive pattern region as long as it can exhibit conductivity in the conductive pattern region.

(measurement of insulation resistance)

2 needle probes were arranged at intervals of 5mm in an insulating region containing cuprous oxide and a phosphorus-containing organic substance as an unfired portion of each sample after firing. The resistance value was evaluated by applying a voltage of 500V for 1 minute between 2 pin probes using an insulation resistance tester TOS7200 manufactured by chrysanthemi water electronics corporation. The evaluation criteria are as follows.

O: 5000MΩ or more

Delta: 1M omega or more and less than 5000M omega

X: less than 1MΩ

(average particle diameter)

The average primary particle diameter of the cuprous oxide fine particles can be measured by a transmission electron microscope or a scanning electron microscope. Specific operations will be described. The sample was cut to an appropriate size and subjected to a wide ion beam (BIB) process using an ion milling apparatus E-3500 manufactured by Hitachi High-Technologies. At this time, the sample is subjected to BIB processing with cooling as needed. The processed sample was subjected to a conductive treatment, and the cross section of the conductive adhesive portion was observed by a scanning electron microscope S-4800 manufactured by Hitachi Corp. The average primary particle diameter is measured for all primary particle diameters in an image in which 10 or more primary particles exist in 1 field of view.

The average secondary particle diameter of the cuprous oxide fine particles can be measured by a transmission electron microscope or a scanning electron microscope. Specific operations will be described. The sample was cut to an appropriate size, and BIB processing was performed using an ion milling apparatus E-3500 manufactured by Hitachi High-Technologies, inc. At this time, the sample is subjected to BIB processing with cooling as needed. The processed sample was subjected to a conductive treatment, and the cross section of the conductive adhesive portion was observed by a scanning electron microscope S-4800 manufactured by Hitachi Corp. All secondary particle sizes in an image in which 10 or more secondary particles exist in 1 field of view were measured, and the average value thereof was taken as the average secondary particle size.

(load deformation temperature)

The load deformation temperature of the support can be measured by a method according to JIS 7191.

(measurement of content of cuprous oxide particles, copper powder and phosphorus-containing organic substance (vol%))

The content (volume%) of the copper powder and the phosphorus-containing organic material in the insulating region in the layer was measured by observing the cross section of the layer disposed on the support by a Scanning Electron Microscope (SEM).

Fig. 11 is an electron micrograph showing a cross section of a layer disposed on a support in the embodiment. As shown in fig. 11, in the electron micrograph, the brighter the material having a higher electron density is observed, and therefore, the brighter the inorganic substance than the organic substance and the brighter the conductive metal than the oxide are observed. Thus, in a certain observation area in the layer of the electron micrograph, the shape, size and contrast can be used to distinguish between cuprous oxide particles of the inorganic substance and copper powder (hereinafter referred to as "all particles") and the phosphorus-containing organic substance. The quotient of the area occupied by all particles in an image of the cross section of the layer included in the observation area (hereinafter referred to as "cross-sectional image") and the total area of the layer in the cross-sectional image is obtained and multiplied by 100, whereby the content (volume%) of all particles can be found.

The cuprous oxide particles and copper powder can be similarly distinguished by shape, size, and contrast. Therefore, the copper oxide content (vol%) in all the particles can be obtained by obtaining the quotient of the area occupied by the cuprous oxide fine particles in the cross-sectional image and the area occupied by all the particles in the cross-sectional image and multiplying by 100. Further, the content (vol%) of copper powder in all particles can be obtained by obtaining the quotient of the area occupied by copper powder in the sectional image and the area occupied by all particles in the sectional image and multiplying by 100.

The content (vol%) of the phosphorus-containing organic material can be obtained by multiplying the quotient of the area occupied by the phosphorus-containing organic material in the cross-sectional image and the total area of the layers in the cross-sectional image by 100.

The image analysis software may be used for image analysis, and examples thereof include ImageJ (manufactured by national institutes of health). In the example, the cross-sectional image was read into ImageJ, converted into a black-and-white 8-bit image, subjected to default threshold setting, and subjected to particle analysis to determine the content of cuprous oxide particles and copper powder.

(measurement of content of cuprous oxide particles, copper powder and phosphorus-containing organic substance (wt.%))

The content (wt%) can be calculated from the content (vol%) obtained from the sectional image and the specific weights of copper oxide, copper, and phosphorus-containing organic material. The specific gravities of copper oxide, copper and phosphorus-containing organic matter can be the following values, respectively.

Copper oxide: 6.0g/cm ³

Copper: 8.9g/cm ³

Phosphorus-containing organic matter: 1.0g/cm ³

As for materials other than these, numerical values described in chemical views, physical and chemical years and the like can be used.

Based on the content (vol%) of the cuprous oxide particles, copper powder, and phosphorus-containing organic matter in the insulating region in the layer thus obtained, the volume parts of the phosphorus-containing organic matter were calculated, assuming that the total volume of the cuprous oxide particles in the insulating region of the layer, or the total volume of the cuprous oxide particles and copper powder in the case of containing copper powder was 100 volume parts, and are shown in table 2. Similarly, the mass parts of the phosphorus-containing organic matter were calculated assuming that the total mass of the cuprous oxide particles in the insulating region of the layer, or the cuprous oxide particles and the copper powder in the case of containing the copper powder was 100 mass parts, and are shown in table 2.

(support adhesion)

The adhesion between the conductive pattern region obtained by firing and the support was evaluated by visual inspection according to the following evaluation criteria.

O: conductive pattern region and support body in close contact state

Delta: although peeling was observed in a part, the whole was in a state of being adhered to the support

X: the conductive pattern region was peeled off from the support (Table 2)

The shorthand symbols in Table 2 refer to the following compounds, respectively. PET: polyethylene terephthalate resin PEN: polyethylene naphthalate resin

PI: polyimide resin

PP: polypropylene resin

PA: polyamide resin

ABS: acrylonitrile butadiene styrene resin

PE: polyethylene resin

PC: polycarbonate resin

POM: polyacetal resin

PBT: polybutylene terephthalate resin

m-PPE: modified polyphenylene ether resin

PPS: polyphenylene sulfide resin

[ samples 35 to 40]

Using the above-mentioned dispersions (a), (c) and (d), dispersion (j) (precipitate 2.8g, copper powder 0g, organic BYK145 (2.0 g), solvent ethanol 6.6 g), dispersion (k) obtained by adding hydrazine hydrate to dispersion (c) (precipitate 2.8g, copper powder 0g, organic BYK145 (2.0 g), solvent ethanol 6.6g, hydrazine hydrate 0.01 g), dispersion (l) obtained by adding hydrazine hydrate to dispersion (c) (precipitate 2.8g, copper powder 0g, organic BYK145 (2.0 g), solvent ethanol 6.6g, hydrazine hydrate 0.1 g), samples 35 to 40 were obtained in which a coating layer having a thickness of 0.8 μm was formed on a PI film of a support by the same method as in sample 1. The hydrazine mass/copper oxide mass in the dispersions (k) and (l) was 0.003, and the dispersion (l) was 0.03.

The smoothness of the surface of the coating layer of each sample was measured. The arithmetic average height Ra of the length of 1000 μm was measured by using a stylus film thickness measuring instrument (ULVAC DektakXT, co). The evaluation criteria are as follows.

O: ra is less than 30nm

Delta: ra is 30nm or more and less than 100nm

X: ra is 100nm or less

By using an electric scanner, a substrate of a sample in an argon atmosphere was irradiated with laser light (wavelength 532nm, output 0.45W, continuous Wave (CW)) while moving the focal position at a maximum speed of 100 mm/s, thereby obtaining a desired conductive pattern region containing copper in a size of 25mm×1 mm.

The film thickness of the conductive pattern region of each sample was measured. In the measurement method, a part of the conductive pattern region was peeled off to expose the support, and the broken slope of the conductive pattern region remaining on the support was measured by a stylus film thickness measuring instrument (ULVAC DektakXT, co.). The ratio to the unfired insulating region was further calculated.

The surface roughness of the conductive pattern region of each sample was measured. The arithmetic average height Ra of the length of 1000 μm was measured by using a stylus film thickness measuring instrument (ULVAC DektakXT, co). The evaluation criteria are as follows.

O: ra is 50nm or more and less than 200nm

Delta: ra is 20nm or more and less than 50nm, 200nm or more and less than 500nm

X: ra is less than 20nm and more than 500nm

Resistance values were evaluated at both ends of the conductive pattern region by using a 4-terminal measurement method. The evaluation criteria are as follows.

O: resistance value is less than 30 mu omega cm

Delta: the resistance value is more than 30 mu omega cm and less than 100 mu omega cm

X: resistance value is above 100 mu omega cm

(measurement of withstand voltage)

2 conductive pattern regions of the size 25mm×1mm were arranged at 1mm intervals, and voltage resistance was measured for insulating regions containing cuprous oxide and a phosphorus-containing organic substance and containing hydrazine or hydrazine hydrate as unfired portions located therebetween.

In the measurement method, a needle probe was connected to 2 conductive pattern areas, and an ac voltage was applied between 2 needle probes using a voltage endurance tester TOS5300 manufactured by chrysanthemi water electronics industry co. The voltage was slowly increased, and the voltage value at which dielectric breakdown occurred was measured. The evaluation criteria are as follows.

O: the withstand voltage is more than 1.7kV/mm

Delta: the withstand voltage is more than 1kV/mm and less than 1.7kV/mm

The X withstand voltage is less than 1kV/mm

(evaluation results)

[ samples 1 to 25]

In the dispersions (a) to (i), no coagulated precipitate was generated in the visual evaluation, and all of the dispersions were excellent in dispersibility.

In sample 1, although peeling was observed in a part of the conductive pattern region during laser firing, the entire conductive pattern region was adhered to the support, and conductivity was confirmed. In xenon flash firing, the dispersion applied during firing is blown off, failing to obtain a conductive pattern region.

In samples 2 to 4, 7, and 9 to 17, the conductive pattern region was adhered to the support during laser firing, and conductivity was confirmed. In xenon flash firing, the dispersion applied during firing is blown off, failing to obtain a conductive pattern region.

In samples 5 and 6, the content of the phosphorus-containing organic matter in the layer was large, and the result of evaluation of conductivity was Δ. The layer disposed on the support after the firing of cuprous oxide is in a state of adhesion to the support.

In sample 8, a conductive pattern region having excellent conductivity and being in close contact with the support was obtained in both the laser firing and the xenon flash firing.

In the samples 18 and 19, the conductive pattern region was obtained by laser firing, but in the adhesion to the support, a part of the conductive pattern region was peeled off during laser firing.

Samples 20 to 25 had an adhesion layer, and conductive pattern regions in adhesion to the support were obtained in both the laser firing and the xenon flash firing.

[ samples 26 to 34]

As a support, a case having no adhesion layer and having different materials as shown in table 2 was prepared. The shape of the housing is a curved surface body having a mortar shape with a radius of curvature of 500 mm. The dispersion (c) was applied to the prepared shell so that the dry film thickness reached 5 μm by the spray method, to obtain samples 26 to 34. Then, the samples 26 to 34 were irradiated with laser light (wavelength 445nm, output 1.5W, continuous Wave (CW)) using an electric scanner while moving the focal position so that the focal point was focused on the surface of the mortar shape of the case at a maximum speed of 300 mm/min, thereby obtaining a desired conductive pattern region containing copper in a size of 25mm×1mm on the surface of the case. The conductive pattern region thus obtained had fine cracks in a part thereof, but was in close contact with the case, and was excellent in conductivity.

[ samples 35 to 40]

The dispersions (j) (k) (l) were excellent in dispersibility without generating agglomerated precipitates in visual evaluation.

The smoothness of the coating layers of samples 35 to 40 was evaluated. The evaluation results are shown in table 3. Since the light-absorbing layer has smoothness, the light-absorbing layer does not cause irregular reflection on the surface of the coating layer when the light is irradiated, and can appropriately absorb the light.

The resistance values of the conductive pattern regions of the samples 35 to 40 were evaluated. The evaluation results are shown in table 3. In the sample 38, the coating layer was ablated when irradiated with laser light, and a suitable conductive pattern region was not obtained.

The film thickness of the conductive pattern regions of samples 35 to 37, 39, and 40 was measured, and the film thickness ratio to the insulating region that was not fired was calculated. The evaluation results are shown in table 3. The film thickness ratio is in the range of 45 to 50%.

The surface roughness of the conductive pattern regions of the samples 35 to 37, 39, and 40 was evaluated. The evaluation results are shown in Table 3. All have a suitable surface roughness.

Voltage resistance evaluation was performed in the insulating regions of samples 35 to 37, 39, and 40. The evaluation results are shown in table 3. Samples 36, 37, 39, 40 have good withstand voltages.

A resin layer (PET film: cosmosfine A4100, thickness 100 μm, manufactured by Toyobo Co., ltd.) having a function as a sealing layer was disposed in the sample 36. A layer containing silicon oxide was provided as a moisture barrier layer in the resin layer, and a bonding layer (MO series of optical adhesive sheets of Lintec corporation) was provided for bonding with the layer having the conductive pattern region disposed on the support. In order to prevent the mixing of moisture from the edge of the resin layer, the resin layer was sealed with a thermosetting sealing material (AJINOMOTO FINE TECHNO, AES-210). Further, a part of the resin layer was opened to expose the conductive pattern region, and an electrode was provided using low-temperature Solder (ECO solvent LEO, manufactured by kilometals industries, ltd.). In this state, the test was carried out in an environment of 85 ℃ and 85RH% to accelerate the deterioration of the conductivity of the conductive pattern region. The resistance value was evaluated after 1000 hours, and as a result, the resistance change rate was not more than +5%, which was good. This is thought to be because oxidation of phosphorus occurs before copper is oxidized by the action of oxygen and moisture mixed in a minute amount into the sealed interior in the acceleration test, and thus the resistance change of the conductive pattern region is suppressed to be low.

As a sample 41, a glass-made wine glass was prepared as a support having a three-dimensional curved surface. The radius of curvature of the red wine glass is 35mm. The glass was immersed in a container filled with the dispersion (c) and lifted up at a constant speed, whereby a coating layer having a dry film thickness of 2 μm was obtained on the outer surface of the glass. The coating layer was then irradiated with laser light (wavelength 532nm, output 0.22W, pulse repetition frequency 260 kHz) in air at a speed of 20 mm/sec using a laser marker (KEYENCE laser marker MD-S9910A). Thereby, a conductive pattern region containing reduced copper was obtained on the surface of the red wine glass. A photograph thereof is shown in fig. 12A. A schematic diagram thereof is shown in fig. 12B. The obtained conductive pattern region was adhered to glass, and the resistance value of the conductive pattern region was evaluated as "o", and the withstand voltage of the insulating pattern region was evaluated as "o".

Further, in order to obtain copper wiring, the coating layer located in the insulating region as a portion not subjected to laser irradiation is removed using ethanol as a cleaning solvent. The photograph after removal is shown in fig. 12C. The resistance value of the copper wiring after removal was evaluated as good.

In addition, as in the above experiment, as the sample 42, a glass-made wine glass was prepared as a support having a three-dimensional curved surface. The radius of curvature of the red wine glass is 35mm. The glass was immersed in a container filled with the dispersion (c) and lifted up at a constant speed, whereby a coating layer having a dry film thickness of 2 μm was obtained on the outer surface of the glass. The coating layer was then irradiated with laser light (wavelength 355nm, output 0.25W, pulse repetition frequency 300 kHz) at a rate of 20 mm/sec in air using a laser marker (KEYENCE laser marker MD-U1000C) different from the above experiment. Thereby, a conductive pattern region containing reduced copper was obtained on the surface of the red wine glass. The conductive pattern region thus obtained was in close contact with glass, and was excellent in conductivity.

As sample 43, a micro-adhesive PET film (SRL-0753 manufactured by Lintec Co., ltd.) was adhered to the surface of the coating layer of sample 36 as a resin layer having oxygen barrier property, and a laser (wavelength 532nm, output 0.22W, pulse repetition frequency 260 kHz) was irradiated to the coating layer through the resin layer at a speed of 20 mm/sec in air using a laser marker (KEYENCE Co., ltd., laser marker MD-S9910A). After which the resin layer is removed. The obtained conductive pattern region was adhered to the PI film, and the resistance value of the conductive pattern region was evaluated as o, and the withstand voltage of the insulating region was evaluated as o.

Further, a resin layer (PET film: cosmosine A4100, thickness 100um, manufactured by Toyobo Co.) was disposed as a sealing material layer belonging to one example of the other resin layer on the conductive pattern region and the insulating region exposed by removing the resin layer. A layer containing silicon oxide was provided as a moisture barrier layer in the resin layer, and a bonding layer (MO series of optical adhesive sheets of Lintec corporation) was provided for bonding with the layer having the conductive pattern region disposed on the support. In order to prevent the mixing of moisture from the edge of the resin layer, the resin layer was sealed with a thermosetting sealing material (AJINOMOTO FINE TECHNO, AES-210). Further, a part of the resin layer was opened to expose the conductive pattern region, and an electrode was provided at this position using low temperature Solder (ECO solvent LEO, kilometal industries, ltd.). In this state, the test was carried out in an environment of 85 ℃ and 85RH% to accelerate the deterioration of the conductivity of the conductive pattern region. The resistance value was evaluated after 1000 hours, and as a result, the resistance change rate was not more than +5%, which was good. This is thought to be because oxidation of phosphorus occurs before copper is oxidized by the action of oxygen and moisture mixed in a minute amount into the sealed interior in the acceleration test, and thus the resistance change of the conductive pattern region is suppressed to be low.

Comparative example 1

A dispersion (x) containing fine particles of cuprous oxide was obtained by the same operation as that of the dispersion (a), except that polyvinylpyrrolidone (hereinafter referred to as PVP) was used instead of the phosphorus-containing organic substance. The composition of the dispersion (x) was 2.8g of precipitate, 0.2g of polyvinylpyrrolidone, 6.6g of ethanol dispersion medium, and the content of copper oxide in the cuprous oxide fine particles was 100% by volume.

Comparative example 1 was obtained in which a coating layer of dispersion (x) was formed on a PET film (cosmosine a4100 manufactured by eastern spinning corporation) having a thickness of 100 μm as a support in a thickness of 0.5um by the same procedure as in samples 1 to 19.

In comparative example 1, a substrate of a sample was irradiated with laser light (wavelength 445nm, output 1.2W, continuous Wave (CW)) while moving the focal position at a maximum speed of 300 mm/min by using an electric scanner, whereby a conductive pattern region containing copper was obtained in a desired size of 25mm×1 mm.

After firing, 2 pin probes were provided in the insulating region as an unfired portion of comparative example 1 at intervals of 5 mm. The resistance value at this time was evaluated by applying a voltage of 500V for 1 minute between 2 pin probes using an insulation resistance tester TOS7200 manufactured by chrysanthemi water electronics corporation, and as a result, the resistance value was less than 1mΩ, and the insulation was insufficient.

Further, the withstand voltage was measured in the same manner as described above for the insulating region containing cuprous oxide as an unfired portion, and containing no organic substance containing phosphorus and hydrazine or hydrazine hydrate. As a result, the withstand voltage was 0.9kV/mm, which was evaluated as X.

Comparative example 2

Comparative example 2 in which a coating layer was formed on a support PI film ((manufactured by eastern dupont, KAPTON500H thickness 125 μm) at a thickness of 1.0 μm was obtained by the same operation as samples 1 to 19, using Metalon ICI-021, which is a dispersion containing cupric oxide particles, a phosphorus-containing organic matter, and containing hydrazine or hydrazine hydrate, instead of the dispersion containing cuprous oxide particles.

The conductive pattern regions were obtained by irradiating laser light in the same manner as in the samples 35 to 38.

The results of evaluation of the respective items in the same manner as in the samples 35 to 38 are shown in table 3. The smoothness of the coating layer was x. It is believed that in the step of forming the coating layer, the dispersion is poor in wettability with the support, and does not contain hydrazine or hydrazine hydrate and a phosphorus-containing organic substance, so that copper oxide particles in the state of being formed into the coating layer are poor in dispersibility, and aggregation occurs.

The resistance value of the conductive pattern region was x. It is believed that since the smoothness of the coating layer is poor and does not contain hydrazine or hydrazine hydrate and a phosphorus-containing organic substance, reduction and sintering of copper oxide particles cannot be properly performed with laser light.

The film thickness of the conductive pattern region was measured, and the film thickness ratio to the insulating region that was not fired was calculated. The film thickness ratio was 68%.

The surface roughness of the conductive pattern region was x. It is believed that in comparative example 2, since the smoothness of the coating layer was poor and hydrazine or hydrazine hydrate and a phosphorus-containing organic substance were not contained, reduction and sintering of copper oxide particles were not properly performed by laser light, and thus the bonding of particles and the surface was not performed, and the surface was rough. It is believed that the reduction and sintering of the copper oxide particles cannot be performed by the laser even when at least one of hydrazine or hydrazine hydrate and a phosphorus-containing organic substance is not included.

The withstand voltage of the insulating region was evaluated, and as a result, delta was obtained. It is believed that in comparative example 2, since hydrazine or hydrazine hydrate and a phosphorus-containing organic substance are not contained, the dispersibility of the copper oxide particles in the state of the coating layer is poor, and the insulating property cannot be sufficiently exhibited. It is believed that when at least one of hydrazine or hydrazine hydrate and a phosphorus-containing organic substance is not contained, the dispersibility of the copper oxide particles in the state of the coating layer is also poor.

Comparative example 3

Using the dispersion (c), 2 coating layers (thickness 0.8 μm) in which 25mm×1mm patterns were arranged in parallel at 1mm intervals were formed on a support borosilicate glass substrate (SCHOTT company Tempax) by a reverse transfer method. The coating layer was further reduced by a plasma sintering method to obtain 2 conductive pattern regions of 25mm×1mm containing reduced copper and phosphorus.

The voltage resistance was evaluated for the obtained 2 conductive pattern areas, and the result was x. It is believed that this is because the insulating region is not contained but only air is present between the 2 conductive pattern regions, and thus the insulating property cannot be exhibited.

[ measurement of phosphorus in conductive Pattern region ]

After the sample 8 was subjected to laser firing as described above, phosphorus element in the formed conductive pattern region was measured.

1) Sample preparation, XPS measurement

From sample 8 after laser firing, a small piece of about 3mm square was cut, and XPS measurement was performed covering a mask of 5 mm. Phi. In XPS measurement, ar is used ⁺ Ion sputtering was performed for depth direction analysis.

< XPS measurement conditions >

The using device comprises: ULVAC-PHI Versa probeII

Excitation source: mono.AlKα15kV×3.3mA

Analysis size: about 200 μm phi

Photoelectron extraction angle: 45 ° ± 20 °

Taking-in area: cu 2P3/2, P2P, C1 s, O1 s, N1 s

And (3) energy communication: 93.9eV

Acceleration voltage: 3kV

Sample current: 1.6. Mu.A

Sample size: 2mm by 2mm

Sample rotation: has the following components

As a result of XPS measurement, it was confirmed that the content of phosphorus element relative to copper was 0.127atom/atom% in terms of atomic composition percentage and 0.062w/w% in terms of mass percentage in sample 8.

After the samples 35 to 37 were subjected to the laser firing as described above, the phosphorus element in the conductive pattern region formed was measured. The evaluation results are shown in table 3. The elemental concentration ratio of phosphorus/copper in each sample was 0.02 to 0.30. In addition, the carbon element and the nitrogen element in the conductive pattern region were measured in the same manner. The evaluation results are shown in table 3. The elemental concentration ratio of carbon/copper in each sample is 1 to 6. The elemental nitrogen/copper ratio of each sample was 0.04 to 0.6.

Table 3 is shown below.

The present invention is not limited to the above-described embodiments and examples. Modifications and the like of the above-described embodiments and examples may be devised based on the knowledge of those skilled in the art, and the above-described embodiments and examples may be arbitrarily combined, and such modifications and the like are also included in the scope of the present invention.

Industrial applicability

According to the present invention, the manufacturing process can be greatly simplified, and a structure having conductive pattern regions, which has excellent electrical insulation between conductive pattern regions and high reliability, can be provided.

Further, according to the present invention, there is no need for equipment for realizing a vacuum atmosphere or an inert gas atmosphere in the photo-firing treatment of copper oxide, and a laminate and a method for manufacturing the laminate can be provided, which can reduce the manufacturing cost of the structure.

As described above, the structure and the laminate of the present invention can be suitably used for wiring materials, mesh electrodes, electromagnetic wave shielding materials, and heat dissipation materials for electronic circuit boards and the like.

The present application is based on Japanese patent application Nos. 2017-139133, 2017-139134, 2017-141518, 2017-141519, 2017-145188, 2018-023239, 2018-13, and 2018-2017-141519, respectively. These are all incorporated herein.

Claims

1. A laminate is characterized by comprising a support, a coating layer comprising copper oxide and phosphorus disposed on a surface constituted by the support, and a resin layer disposed so as to cover the coating layer.

2. A laminate is characterized by comprising a support, a coating layer disposed on a surface constituted by the support and containing copper oxide and hydrazine or hydrazine hydrate, and a resin layer disposed so as to cover the coating layer.

3. A laminate is characterized by comprising a support, a coating layer which is disposed on a surface constituted by the support and contains copper oxide, phosphorus, and contains hydrazine or hydrazine hydrate, and a resin layer which is disposed so as to cover the coating layer.

4. A laminate is characterized by comprising a support, a layer in which an insulating region containing copper oxide and a phosphorus-containing organic substance and a conductive pattern region containing copper are disposed adjacent to each other on a surface constituted by the support, and a resin layer formed so as to cover the layer.

5. A laminate is characterized by comprising a support, a layer in which an insulating region containing copper oxide and hydrazine or hydrazine hydrate and a conductive pattern region containing copper are disposed adjacent to each other on a surface constituted by the support, and a resin layer formed so as to cover the layer.

6. A laminate is characterized by comprising a support, a layer in which an insulating region containing a hydrazine or hydrazine hydrate and a conductive pattern region containing copper are disposed adjacent to each other, the insulating region containing copper, a phosphorus-containing organic material, and a resin layer formed so as to cover the layer.

7. The laminate according to any one of claims 1 to 6, wherein the copper oxide is fine particles containing the copper oxide, the phosphorus is a phosphorus-containing organic substance, and the content of the phosphorus-containing organic substance is 5 parts by volume or more and 900 parts by volume or less, based on 100 parts by volume of the total volume of the fine particles.

8. The laminate according to any one of claims 1 to 6, wherein the coating layer is disposed on the support having a three-dimensional surface.

9. A copper wiring comprising reduced copper obtained by reducing copper oxide, phosphorus and carbon, wherein the element concentration ratio of phosphorus/copper is 0.02 to 0.30, and the element concentration ratio of carbon/copper is 1.0 to 6.0.

10. The copper wiring according to claim 9, wherein an arithmetic average roughness Ra of the copper wiring surface is 20nm to 500 nm.

11. A method for producing a laminate, characterized by comprising the steps of:

a step of disposing a coating layer containing copper oxide and a phosphorus-containing organic material on a surface constituted by a support; and

and a step of disposing a resin layer so as to cover the coating layer.

12. A method for producing a laminate, characterized by comprising the steps of:

Disposing a coating layer containing copper oxide, hydrazine or hydrazine hydrate on a surface constituted by a support; and

and a step of disposing a resin layer so as to cover the coating layer.

13. A method for producing a laminate, characterized by comprising the steps of:

disposing a coating layer containing copper oxide, a phosphorus-containing organic material, and hydrazine or hydrazine hydrate on a surface constituted by a support; and

and a step of disposing a resin layer so as to cover the coating layer.

14. The method for producing a laminate according to claim 11, further comprising the steps of:

and a step of selectively irradiating the coating layer with light by either the resin layer or the support, and disposing a layer in which an insulating region containing copper oxide and a phosphorus-containing organic material and a conductive pattern region containing copper are adjacent to each other on a surface constituted by the support.

15. The method for producing a laminate according to claim 12, further comprising the steps of:

and a step of selectively irradiating the coating layer with light by either the resin layer or the support, and disposing a layer in which an insulating region containing copper oxide and hydrazine or hydrazine hydrate and a conductive pattern region containing copper are adjacent to each other on a surface constituted by the support.

16. The method for producing a laminate according to claim 11, further comprising the steps of:

and a step of selectively irradiating the coating layer with light by either the resin layer or the support, wherein a layer including copper oxide, a phosphorus-containing organic material, an insulating region including hydrazine or hydrazine hydrate, and a conductive pattern region including copper are disposed adjacent to each other on a surface constituted by the support.

17. The method for producing a structure according to any one of claims 14 to 16, wherein the light is laser light having a center wavelength of 355nm to 532 nm.